JP6896718B2 - Curable composition, cured film, color filter, light-shielding film, solid-state image sensor, image display device, and method for manufacturing the cured film. - Google Patents

Description

The present invention relates to a curable composition, a cured film, a color filter, a light-shielding film, a solid-state image sensor, an image display device, and a method for producing a cured film.

The color filter used in the liquid crystal display device is provided with a light-shielding film called a black matrix for the purpose of blocking light between colored pixels and improving contrast.
Further, the solid-state image sensor is also provided with a light-shielding film for the purpose of preventing noise generation, improving image quality, and the like. Currently, mobile terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with a small and thin imaging unit. Such an image pickup unit generally includes a solid-state image sensor such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, a lens for forming a subject image on the solid-state image sensor, and the like. It has.

Patent Document 1 is characterized by containing a black colorant and a resin component having an average particle diameter of 40 nm or less, which can form a coating film arranged on the periphery of an effective pixel region (imaging portion) of a solid-state image sensor. The composition for forming a light-shielding film is described as "a composition for forming a light-shielding film", wherein "a black colorant contains at least one of carbon black and titanium black".

Japanese Unexamined Patent Publication No. 2006-156801

The present inventors examined a light-shielding film obtained by curing the light-shielding film-forming composition described in Patent Document 1, and found that although it has excellent light-shielding properties, there is room for further improvement in the obtained pattern shape. It was revealed that there is. Specifically, the light-shielding film obtained by curing the light-shielding film-forming composition described in Patent Document 1 may have a smaller film thickness at the edges than the film thickness at the center. It was revealed that there was.

Therefore, an object of the present invention is to provide a curable composition capable of obtaining a cured film having an excellent pattern shape while maintaining excellent light-shielding properties.
The present invention also provides a cured film obtained by using the curable composition, a color filter containing the cured film, a light-shielding film, a solid-state image sensor, an image display device, and a method for producing the cured film. It is also an issue to do.

The present inventors have diligently studied to achieve the above-mentioned problems. As a result, a curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, and a cured film obtained by curing the curable composition is visible. The present invention has been completed by finding that a curable composition having an optical density of 4.0 or more per 1.5 μm film thickness in the optical region can solve the above problems.
That is, it was found that the above-mentioned problems can be achieved by the following configuration.

[1] A curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, which is visible in a cured film obtained by curing the curable composition. A curable composition having an optical density of 4.0 or more per 1.5 μm film thickness in the optical region.
[2] The curable composition according to [1], wherein the content of the colorant is 55% by mass or more with respect to the total solid content of the curable composition.
[3] The curable composition according to [1] or [2], wherein the content of the polyfunctional thiol compound is 1 to 5.5% by mass with respect to the content of the colorant.
[4] The curable composition according to any one of [1] to [3], which further contains a polymerization inhibitor.
[5] The curable composition according to [4], wherein the content of the polymerization inhibitor is 0.1 to 1.5% by mass with respect to the content of the polyfunctional thiol compound.
[6] The curable composition according to [4] or [5], wherein the polymerization inhibitor contains a phenolic compound.
[7] The curable composition according to any one of [4] to [6], wherein the polymerization inhibitor contains two or more kinds of phenolic compounds.
[8] The curable composition according to any one of [4] to [7], wherein the polymerization inhibitor contains a hindered amine compound.
[9] The curable composition according to any one of [1] to [8], wherein the colorant is an inorganic pigment.
[10] The inorganic pigment is at least one selected from the group consisting of a metal pigment containing titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin, and a metal pigment containing silver and tin. The curable composition according to [9].
[11] The curable composition according to any one of [1] to [10], wherein the polyfunctional thiol compound is a compound having two or more groups represented by the formula (1).
[12] The curable composition according to any one of [1] to [11], wherein the polyfunctional thiol compound is trifunctional or higher.
[13] The polyfunctional thiol compound is at least one selected from the group consisting of pentaerythritol tetra (3-mercaptopropionate) and trimethylolpropanetris (3-mercaptopropionate) [1]. ] To [12]. The curable composition according to any one of.
[14] The curability according to any one of [1] to [13], wherein the content of the photopolymerization initiator is more than 1% by mass and less than 10% by mass with respect to the total solid content of the curable composition. Composition.
[15] The curing according to any one of [1] to [14], wherein the content of the polymerizable compound is more than 3.5% by mass and less than 20% by mass with respect to the total solid content of the curable composition. Sex composition.
[16] The curing according to any one of [1] to [15], which further contains a dispersant and the content of the dispersant is 17% by mass or more based on the total solid content of the curable composition. Sex composition.
[17] The curable composition according to any one of [1] to [16], wherein the photopolymerization initiator is an oxime compound.
[18] A cured film obtained by curing the curable composition according to any one of [1] to [17].
[19] A color filter containing the cured film according to [18].
[20] A light-shielding film containing the cured film according to [18].
[21] A solid-state image sensor containing the cured film according to [18].
[22] An image display device containing the cured film according to [18].
[23] A curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of [1] to [17], and a curable composition layer. A method for producing a cured film containing an exposure step and an exposure process.
[24] The method for producing a cured film according to [23], wherein the exposure amount of the curable composition layer in the exposure step is 200 mJ / cm ^{2 or more.}
[25] The curable composition layer forming step comprises a coating step of directly coating the curable composition on the support to form a curable composition layer on the support [23] or [24]. The method for producing a cured film according to.
[26] Further, any one of [23] to [25], which comprises a developing step of developing the exposed curable composition layer and a washing step of washing the developed curable composition layer. The method for producing a cured film according to.

According to the present invention, it is possible to provide a curable composition capable of obtaining a cured film having an excellent pattern shape while maintaining excellent light-shielding properties.
According to the present invention, there is provided a cured film obtained by using the curable composition, a color filter containing the cured film, a light-shielding film, a solid-state image sensor, an image display device, and a method for producing the cured film. You can also do it.

It is sectional drawing which shows typically the manufacturing process of the cured film using the curable composition which does not contain a polyfunctional thiol compound for each step. It is sectional drawing which shows typically the manufacturing process of the cured film using the curable composition which does not contain a polyfunctional thiol compound for each step. It is sectional drawing which shows typically the manufacturing process of the cured film using the curable composition which does not contain a polyfunctional thiol compound for each step. It is sectional drawing which shows typically the manufacturing process of the cured film using the curable composition which concerns on embodiment of this invention for each step. It is sectional drawing which shows typically the manufacturing process of the cured film using the curable composition which concerns on embodiment of this invention for each step. It is sectional drawing which shows typically the manufacturing process of the cured film using the curable composition which concerns on embodiment of this invention for each step.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes those that do not contain a substituent and those that contain a substituent. For example, the "alkyl group" includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
Further, the “active light” or “radiation” in the present specification refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV), X-rays, and X-rays. It means an electron beam or the like. Further, in the present specification, "light" means active light rays and radiation. Unless otherwise specified, the term "exposure" as used herein refers to not only the emission line spectrum of a mercury lamp and exposure with far ultraviolet rays, X-rays, EUV light, etc. represented by an excimer laser, but also electron beam, ion beam, etc. Also includes drawing with particle beams.
Further, in the present specification, "(meth) acrylate" represents acrylate and methacrylate. Further, in the present specification, "(meth) acrylic" represents acrylic and methacryl. Further, in the present specification, "(meth) acryloyl" represents acryloyl and methacryloyl. Further, in the present specification, "(meth) acrylamide" represents acrylamide and metaacrylamide. Further, in the present specification, "monomer" and "monomer" are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. A polymerizable group is a group involved in a polymerization reaction.

[Curable composition]
The curable composition contains a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound, and is a cured film obtained by curing the curable composition in the visible light region. The optical density per 1.5 μm thickness is 4.0 or more.
According to the curable composition having such a structure, a cured film having an excellent pattern shape can be obtained while maintaining excellent light-shielding properties (hereinafter, also referred to as "effect of the present invention").
The mechanism by which the effect of the present invention is obtained by the above curable composition is not always clear, but the present inventors speculate as follows. The mechanism by which the curable composition exerts the effect of the present invention is not limited by the following assumptions.

Conventionally known curable compositions containing a colorant such as carbon black and not containing a polyfunctional thiol compound have been widely used because they can obtain a high light-shielding concentration over a wide wavelength range. However, the optical density of the curable composition layer (also referred to as OD: optical density)
Gradually increases from the long wavelength side to the short wavelength side, and the optical density in the short wavelength region is extremely high as compared with the long wavelength side. Therefore, when the curable composition layer is pattern-exposed with light in the ultraviolet region such as g-line, h-line, and i-line, the light does not reach the inside of the curable composition layer, resulting in insufficient exposure. The pattern shape sometimes deteriorated.
The mechanism by which the pattern shape deteriorates due to the above will be described with reference to FIGS. 1 to 6 in which the manufacturing process of the cured film is schematically shown for each process. First, FIGS. 1 to 3 are cross-sectional views schematically showing the manufacturing process of a cured film using a curable composition containing no polyfunctional thiol for each step.
First, as shown in FIG. 1, a curable composition layer 102 is formed on the support 101 using the curable composition. Next, the curable composition layer 102 is exposed through the opening of the photomask 103 (in FIG. 1, the arrow indicates the light irradiation direction, and the lines AB are the edges of the opening of the photomask. It is an extension of. The same shall apply hereinafter.) Next, the curable composition layer 102 after the exposure is developed to form a patterned cured film 201.
Since the optical density of the curable composition layer 102 is high during the exposure during the above procedure, it is difficult for the light to reach the inside of the curable composition layer 102 during the exposure, and the exposure is insufficient under the curable composition layer 102. It becomes. Then, when the development is performed, the curable composition elutes in the portion of the curable composition layer 102 that is insufficiently exposed (FIG. 2). If the post-baking treatment for heating the cured film 201 is performed in such a state, a problem called "heat sagging" occurs in the portion eluted during development. That is, it is presumed that the film thickness at the end portion of the obtained cured film 301 after post-baking is reduced as compared with the central portion (FIG. 3).

4 to 6 are cross-sectional views schematically showing the manufacturing process of a cured film using the curable composition of the present invention for each step.
First, as shown in FIG. 4, a curable composition layer 401 is formed on the support 101 using the curable composition of the present invention. Next, the curable composition layer 401 is exposed through the opening of the photomask 103.
At this time, since the curable composition layer 401 contains a polyfunctional thiol compound, it is presumed that the inside of the curable composition layer 401 is sufficiently cured for the following reasons.
Inside the exposed curable composition layer 401, a radical polymerization reaction is initiated by the photopolymerization initiator. At this time, radicals generated by the photopolymerization initiator may react with oxygen in the curable composition layer 401 to generate peroxy radicals. Since the peroxy radical does not have an action of advancing the polymerization reaction, the polymerization reaction is stopped there.
On the other hand, when the polyfunctional thiol compound is present in the curable composition layer 401, the thiol group in the polyfunctional thiol compound donates hydrogen to the peroxy radical to generate a chile radical that is less susceptible to polymerization inactivation due to oxygen. Then, the polymerization reaction proceeds. Therefore, it is presumed that the curable composition containing the polyfunctional thiol compound is easily sufficiently cured to the inside of the curable composition layer 401.
Further, the optical density of the cured film obtained by curing the curable composition per 1.5 μm film thickness in the visible light region is 4.0 or more, and the curable composition layer 401 has high light-shielding property.
Normally, the light irradiated to the curable composition layer 401 through the opening of the photomask 103 is diffracted at the opening of the photomask 103, and is also irradiated to the mask light-shielding portion 402 outside the AB line. (This is called "leakage light".) If the light-shielding property of the curable composition layer is low, the curable composition layer of the mask light-shielding portion is exposed by the leaked light, which leads to deterioration of the pattern shape.
However, since the curable composition layer 401 has a high light-shielding property, the leaked light is absorbed without exposing the mask light-shielding portion 402 (FIG. 4).
Therefore, when the cured film after the exposure is developed, the cured film 501 having an excellent pattern shape can be obtained because the cured film is sufficiently cured to the inside and the light diffracted at the opening of the photomask is absorbed (FIG. 5). Since this cured film 501 is less likely to cause "heat sagging" even after being post-baked, the difference in film thickness between the central portion and the end portion of the cured film 601 after post-baking is small, and an excellent pattern shape is obtained. It is presumed to have (Fig. 6).

[Optical density (OD value)]
The optical density per 1.5 μm film thickness in the visible light region of the cured film obtained by curing the curable composition is 4.0 or more. Among them, the optical density is more preferably 4.1 or more, further preferably 4.3 or more, in that a curable composition having a more excellent effect of the present invention can be obtained. The upper limit is not particularly limited, but is generally preferably 8.0 or less.
In the present specification, the optical density means the optical density measured by the method described in the examples, and the visible light region means light having a wavelength of 400 to 800 nm. Therefore, the optical density per 1.5 μm film thickness in the visible light region is intended to be 4.0 or more per 1.5 μm film thickness in the entire wavelength range of 400 to 800 nm.

Hereinafter, aspects of each component contained in the curable composition will be described in detail.

[Colorant]
The curable composition contains a colorant. The colorant is at least one selected from the group consisting of pigments and dyes.
The content of the colorant is preferably 55% by mass or more, more preferably 56% by mass or more, and further preferably 58% by mass or more with respect to the total solid content of the curable composition. ..
When the content of the colorant is 55% by mass or more, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
The upper limit of the content of the colorant is not particularly limited, but is generally preferably 70% by mass or less with respect to the total solid content of the curable composition. When the colorant content is below the upper limit, the curable composition has better coatability.

<Pigment>
The pigment is not particularly limited, and known inorganic pigments and / or organic pigments can be used. Among them, the pigment is preferably an inorganic pigment in that a curable composition having a more excellent effect of the present invention can be obtained.

(Inorganic pigment)
The inorganic pigment is not particularly limited, and a known inorganic pigment can be used.
Examples of inorganic pigments include zinc flower, lead white, lithopon, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead tan, iron oxide red, chrome yellow, and zinc yellow (one type of zinc yellow, Zinc yellow 2 types), Ultramarine blue, Prussian blue (ferrous iron potassium) zircon gray, placeojim yellow, chrome titanium yellow, chrome green, peacock, Victoria green, Prussian blue (unrelated to Prussian blue), vanadium zirconium blue, Examples include chrome tin pink, ceramic test red, and salmon pink. Further, as the black inorganic pigment, a metal oxide containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. , Metallic nitrogen substances can be mentioned.

As the inorganic pigment, carbon black, titanium black, a metal pigment and the like (hereinafter, "black pigment") can be obtained in that a curable composition capable of forming a cured film having at least a high optical density can be obtained. Also referred to as) is preferable. Examples of the metal pigment include metal oxidation containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Examples include substances or metallic nitrogen substances.
The inorganic pigment contains at least one selected from the group consisting of a metal pigment containing titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin, and a metal pigment containing silver and tin. It is more preferable to contain at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, and vanadium nitride.
As the inorganic pigment, carbon black can also be used. Specific examples of carbon black include commercially available C.I. I. Pigment Black 1 and other organic pigments C.I. I. Examples include, but are not limited to, inorganic pigments such as Pigment Black 7.

In the curable composition, a pigment having infrared absorption other than the pigment described as the black pigment can also be used.
As the pigment having infrared absorption, a tungsten compound, a metal boride and the like are preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding property in a wavelength in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of the photopolymerization initiator and visible light region, which are related to curing efficiency by exposure.

These pigments may be used in combination of two or more, or may be used in combination with a dye described later. To adjust the tint and to enhance the light-shielding property in the desired wavelength region, for example, a pigment having black or infrared light-shielding property is chromatic colors such as red, green, yellow, orange, purple, and blue. Examples thereof include a mode in which a pigment or a dye described later is mixed. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black or infrared light-shielding pigment, and more preferably to mix a red pigment with a black or infrared light-shielding pigment.
Further, a near-infrared absorber and an infrared absorber, which will be described later, may be added.

The black pigment preferably contains titanium black and / or niobium nitride. Titanium black is black particles containing a titanium atom. It is preferably low-order titanium oxide, titanium oxynitride, titanium nitride or the like. The surface of the titanium black particles can be modified as needed for the purpose of improving dispersibility, suppressing cohesiveness, and the like. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can also be treated with a water-repellent substance as shown in JP-A-2007-302836. It is possible.
Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of the individual particles are small. The same applies to niobium nitride.
Specifically, those having an average primary particle diameter in the range of 10 nm to 45 nm are preferable.

The average primary particle size of the pigment can be measured using a transmission electron microscope (TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
Maximum length (Dmax: maximum length at two points on the contour of the particle image) and maximum length vertical length (DV-max: two straight lines parallel to the maximum length) of the particle image obtained using a transmission electron microscope. When the image was sandwiched between the two straight lines, the length was measured (the shortest length connecting the two straight lines vertically), and the synergistic average value (Dmax × DV-max) 1/2 was taken as the particle diameter. The particle size of 100 particles was measured by this method, and the arithmetic mean value was used as the average particle size to obtain the average primary particle size of the pigment.

The specific surface area of titanium black and niobium nitride is not particularly limited, but BET (Brunauer, Emmett, Teller) has a predetermined performance in terms of water repellency after surface treatment of titanium black and niobium nitride with a water repellent agent. The value measured by the method) ^{is preferably 5 m 2} / g or more and 150 m ² / g or less, and ^{more preferably 20 m 2} / g or more and 120 m ² / g or less.
Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13RN, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilac. Examples thereof include D (trade name, manufactured by Ako Kasei Co., Ltd.) and titanium nitride 50 nm (trade name, manufactured by Wako Pure Chemical Industries, Ltd.).

It is preferable to use titanium oxynitride, titanium nitride or niobium oxynitride as the colorant, and titanium nitride or niobium oxynitride is more preferable, and niobium oxynitride is further preferable because the obtained cured film has better moisture resistance. preferable. It is considered that this is because these colorants are hydrophobic.

Further, it is also preferable to contain titanium black as a dispersant containing titanium black and Si atoms.
In this form, titanium black is contained as a dispersion in the curable composition, and the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is 0 in terms of mass. 05 or more is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is further preferable.
Here, the dispersant includes both those in which titanium black is in the state of primary particles and those in which titanium black is in the state of aggregates (secondary particles).
In order to change the Si / Ti of the dispersion to be dispersed (for example, to set it to 0.05 or more), the following means can be used.
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is reduced at a high temperature (for example, 850 to 1,000 ° C.) to obtain titanium black particles. A dispersant containing Si and Ti as a main component can be obtained. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo Co., Ltd.).
Commercially available products of silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik) and the like.
A dispersant may be used to disperse the titanium oxide and the silica particles. Examples of the dispersant include those described in the column of dispersants described later.
The above dispersion may be carried out in a solvent. Examples of the solvent include water and organic solvents. Examples thereof will be described in the column of organic solvent described later.
Titanium black in which Si / Ti is adjusted to, for example, 0.05 or more is prepared by, for example, the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of JP-A-2008-266045. can do.

By adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersant containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), curing including this disperse is performed. When the cured film is formed using the sex composition, the residue derived from the curable composition outside the formed region of the cured film is reduced. The residue contains components derived from a curable composition such as titanium black particles and a resin component.
The reason why the residue is reduced is not yet clear, but the dispersant as described above tends to have a smaller particle size (for example, a particle size of 30 nm or less), and further contains Si atoms of the disperse. By increasing the number of components, the adsorptivity of the entire film to the substrate is reduced. It is presumed that this contributes to the improvement of the developability of the uncured curable composition (particularly titanium black) in the formation of the cured film.
Since titanium black is excellent in light blocking light in a wide wavelength range from ultraviolet light to infrared light, the above-mentioned dispersant containing titanium black and Si atom (preferably Si / Ti is 0 in terms of mass). The cured film formed using (0.05 or more) exhibits excellent light-shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is determined by, for example, the method (1-1) or method (1-2) described in paragraph 0033 of JP2013-249417A. ) Can be used for measurement.
Whether or not the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersant contained in the cured film obtained by curing the curable composition is 0.05 or more. In order to determine, the method (2) described in paragraph 0035 of JP2013-249417A can be used.

In the dispersant containing titanium black and Si atom, the above-mentioned titanium black can be used.
In this dispersant, in addition to titanium black, for the purpose of adjusting dispersibility, colorability, etc., composite oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black, etc. A black pigment composed of 1 type or a combination of 2 or more types may be used. In this case, it is preferable that the dispersant made of titanium black occupies 50% by mass or more of the total dispersoid.
In this dispersion, for the purpose of adjusting the light-shielding property, other colorants (organic pigments and / or dyes, etc.) may be used in combination with titanium black as long as the effects of the present invention are not impaired. Good.
Hereinafter, the materials used when introducing Si atoms into the dispersion to be dispersed will be described. When introducing a Si atom into the dispersion, a Si-containing substance such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, synthetic silica, and the like, which may be appropriately selected and used.
Further, when the particle size of the silica particles is smaller than the film thickness when the cured film is formed, the light-shielding property is more excellent, so that it is preferable to use fine particle type silica. Examples of the fine particle type silica include the silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.

The curable composition can use a tungsten compound and / or a metal boride as a pigment.
Tungsten compounds and metal borides have high absorption for infrared rays (light with a wavelength of about 800 to 1200 nm) (that is, high light-shielding property (shielding property) for infrared rays) and absorption for visible light. It is a low infrared shielding material. Therefore, by containing the tungsten compound and / or the metal boride, the curable composition of the present invention can form a pattern having high light-shielding property in the infrared region and high translucency in the visible light region.
Tungsten compounds and metal borides absorb less light than the visible range used for exposure, such as high-pressure mercury lamps, KrF, and ArF, which are used for image formation. Therefore, by combining with a polymerizable compound, an alkali-soluble resin, and a photopolymerization initiator described later, an excellent pattern can be obtained, and a development residue can be further suppressed in pattern formation.

Examples of the tungsten compound include a tungsten oxide-based compound, a tungsten booxide-based compound, and a tungsten sulfide-based compound, and the tungsten oxide-based compound represented by the following general formula (composition formula) (I) is preferable.
M _x W _{y Oz} ... (I)
M stands for metal, W stands for tungsten, and O stands for oxygen.
0.001 ≤ x / y ≤ 1.1
2.2 ≤ z / y ≤ 3.0

Examples of the metal of M include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, and the like. Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, Rb, Cs and the like can be mentioned, but alkali metals are preferable. The metal of M may be one kind or two or more kinds.

M is preferably an alkali metal, more preferably Rb or Cs, and even more preferably Cs.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, the formation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
When z / y is 2.2 or more, the chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , and Ba _0.33 WO _3. Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

The tungsten compound is preferably fine particles. The average primary particle size of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average primary particle size is in such a range, the tungsten fine particles are less likely to block visible light due to light scattering, so that the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, it is preferable that the average primary particle size is small, but for reasons such as ease of handling during production, the average primary particle size of the tungsten fine particles is usually 1 nm or more.

Two or more kinds of tungsten compounds can be used.

Tungsten compounds are available commercially. When the tungsten compound is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Patent No. 4096205). ..
The tungsten oxide-based compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Metal borides include lanthanum boride (LaB ₆ ), _{placeodium boride (PrB 6} ), neodium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium borides (YB ₆ ), and titanium borides (YB 6). TiB ₂ ), Zirconium _{Boride (ZrB 2} ), Hafnium Boride (HfB ₂ ), Vanadium _{Boride (VB 2} ), _{Tantal Boride (TaB 2} ), Chromium Boride (CrB, CrB ₂ ), Molybdenum Boride (CrB, CrB 2) One or more of MoB ₂ , Mo ₂ B ₅ , MoB), tungsten borides (W ₂ B ₅ ) and the like can be mentioned, and lanthanum boride (LaB ₆ ) is preferable.

The metal boride is preferably fine particles. The average primary particle size of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. When the average primary particle size is in such a range, the metal borohydride fine particles are less likely to block visible light due to light scattering, so that the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, it is preferable that the average primary particle size is small, but the average primary particle size of the metal boride fine particles is usually 1 nm or more for reasons such as ease of handling during production.

Two or more kinds of metal borides can be used.

The metal boride is available as a commercially available product, and is also available as a dispersion of fine metal boride particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.

(Titanium nitride-containing particles)
As the inorganic pigment, titanium nitride-containing particles containing an Fe atom can also be used. The vapor phase reaction method is usually used for producing the titanium nitride-containing particles, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because of the fact that impurities are less mixed, the particle size is easily uniform, and the productivity is high.
Examples of the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, high frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less contamination of impurities from the electrodes is preferable. As a specific method for producing titanium nitride-containing fine particles by the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and the titanium powder is nitrided in the cooling process. , A method of synthesizing titanium nitride-containing particles and the like. The thermal plasma method is not limited to the above.

The method for producing the titanium nitride-containing particles is not particularly limited, but the production methods described in paragraphs <0037> to <089> of International Publication No. 2010/147098 can be referred to. For example, instead of the Ag powder of International Publication No. 2010/147098, a component containing Fe and / or a component containing Si, which will be described later, is used, and a mixture of this and a titanium powder material (titanium particles) is used as a raw material. , Titanium nitride-containing particles contained in the curable composition of the present invention can be produced.

The titanium powder material (titanium particles) used for producing the titanium nitride-containing particles is preferably of high purity. The titanium powder material is not particularly limited, but a material having a purity of titanium element of 99.99% or more is preferable, and a material having a purity of 99.999% or more is more preferably used.

The titanium powder material (titanium particles) used for producing titanium nitride-containing particles may contain atoms other than titanium atoms. Other atoms that can be contained in the titanium powder material include, for example, Fe atom and Si atom.
When the titanium powder material contains Fe atoms, the content of Fe atoms is preferably more than 0.001% by mass with respect to the total mass of the titanium powder material.
When the titanium powder material contains Si atoms, the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass, preferably 0.01, based on the total mass of the titanium powder material. It is more preferably ~ 0.15% by mass, and further preferably 0.02 to 0.1% by mass. When the content of Si atom is more than 0.002% by mass, the patterning property of the cured film is further improved. When the content of Si atom is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is more stabilized. As a result, when the titanium nitride-containing particles are dispersed, the adsorptivity of the dispersant to the titanium nitride-containing particles is improved, the undispersed substances of the titanium nitride-containing particles are reduced, and the generation of particles can be suppressed. Be done.
The water content in the titanium powder material (titanium particles) used for producing the titanium nitride-containing particles is preferably less than 1% by mass and less than 0.1% by mass with respect to the total mass of the titanium powder material. It is more preferable, and it is further preferable that it is substantially not contained.

The titanium nitride-containing particles can be obtained by using the thermal plasma method to obtain a diffraction angle of 2θ (details will be described later) of the peak derived from the (200) plane when CuKα ray is used as an X-ray source, and 42.6. It becomes easy to adjust to the range of more than ° and less than 43.5 °.

The method for incorporating the Fe atom into the titanium nitride-containing particles is not particularly limited, and for example, the Fe atom is introduced at the stage of obtaining the titanium particles (titanium powder) used as the raw material of the above-mentioned titanium nitride-containing particles. The method etc. can be mentioned. More specifically, when titanium is produced by the Kroll process or the like, a reaction vessel made of a material containing Fe atoms such as stainless steel (SUS) is used, or a press machine for crushing titanium and a press machine for crushing titanium. Fe atoms can be attached to the surface of titanium particles by using a material containing Fe atoms as the material of the crusher.
When the thermal plasma method is used to produce titanium nitride-containing particles, components such as Fe particles and Fe oxides are added in addition to the titanium particles as a raw material, and these are nitrided by the thermal plasma method. , Fe atom can be contained in the titanium nitride-containing particles.
The Fe atoms contained in the titanium nitride-containing particles include ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, and sulfides. And acid sulfide, etc., may be contained in any form. Fe atoms contained in the titanium nitride-containing particles may be present as impurities at the positions between the crystal lattices, or may be present as impurities at the grain boundaries in an amorphous state.

As a result of diligent studies, the present inventors have found that the content of Fe atoms in the titanium nitride-containing particles is related to the patterning property and the corrosion resistance of the electrode. It is considered that the Fe atom contained in the titanium nitride-containing particles has excellent adhesion to the electrode and the substrate, and the titanium nitride in the titanium nitride-containing particles adheres to the electrode and the substrate via the Fe atom. It is considered that Fe atoms remain on the electrode and the substrate after patterning of the cured film such as development treatment, and titanium nitride is easily removed. Therefore, it is presumed that the patterning property of the cured film is improved by increasing the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more. On the other hand, if the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrode and the substrate increases, which is considered to cause corrosion of the electrode. Therefore, it is presumed that the corrosion resistance of the electrode is improved by reducing the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less.
The content of Fe atoms in the titanium nitride-containing particles is preferably more than 0.001% by mass and less than 0.4% by mass with respect to the total mass of the titanium nitride-containing particles. Of these, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable. When the content of Fe atoms is more than 0.001% by mass, the patterning property of the cured film is further improved. When the content of Fe atoms is less than 0.4% by mass, the corrosion resistance of the electrode by the cured film is further improved (the cured film can suppress corrosion of the electrode). That is, when the content of Fe atoms in the titanium nitride-containing particles is within the above range, excellent patterning property of the cured film and corrosion resistance of the electrode can be obtained.
The content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma) emission spectroscopic analysis.

The titanium nitride-containing particles preferably further contain a Si atom (silicon atom). As a result, the patterning property of the cured film is further improved. The reason why the patterning property is improved by containing the Si atom is considered to be the same as that of the Fe atom described above.
The content of Si atoms in the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass, preferably 0.01 to 0.15, based on the total mass of the titanium nitride-containing particles. It is more preferably mass%, and even more preferably 0.02 to 0.1 mass%. When the content of Si atom is more than 0.002% by mass, the patterning property of the cured film is further improved. When the content of Si atom is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles is more stabilized. As a result, when the titanium nitride-containing particles are dispersed, the adsorptivity of the dispersant to the titanium nitride-containing particles is improved, the undispersed substances of the titanium nitride-containing particles are reduced, and the generation of particles can be suppressed. Be done.
The content of Si atoms in the titanium nitride-containing particles can be measured by the same method as the Fe atoms described above.

The method for incorporating the Si atom into the titanium nitride-containing particles is not particularly limited, and for example, the Si atom is introduced at the stage of obtaining the titanium particles (titanium powder) used as the raw material of the titanium nitride-containing particles described above. The method etc. can be mentioned. More specifically, when titanium is produced by the Kroll process or the like, a reaction vessel made of a material containing Si atoms is used, or a Si atom is used as a material for a press machine and a crusher for crushing titanium. Si atoms can be attached to the surface of the titanium particles by using a substance containing the above.
When the thermal plasma method is used to produce titanium nitride-containing particles, components such as Si particles and Si oxides are added in addition to the titanium particles as a raw material, and these are nitrided by the thermal plasma method. , The titanium nitride-containing particles can contain Si atoms.
Si atoms contained in titanium nitride-containing particles include ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, nitrides, sulfides and acid sulfides. Etc., it may be included in any form. The Si atom contained in the titanium nitride-containing particles may be present as an impurity at the position between the crystal lattices, or may be present as an impurity at the crystal grain boundary in an amorphous state.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass, preferably 15 to 75% by mass, based on the total mass of the titanium nitride-containing particles. More preferably, it is 20 to 70% by mass. The content of Ti atoms in the titanium nitride-containing particles can be measured by ICP emission spectroscopic analysis.
The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 3 to 60% by mass, preferably 5 to 50% by mass, based on the total mass of the titanium nitride-containing particles. More preferably, it is 10 to 40% by mass. The content of nitrogen atoms can be analyzed by the inert gas melting-thermal conductivity method.
The titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and are usually noticeable when oxygen is mixed during the synthesis or when the particle size is small, but due to oxidation of the particle surface or the like. , Some oxygen atoms may be contained.
The content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass, based on the total mass of the titanium nitride-containing particles. It is more preferably ~ 30% by mass. The content of oxygen atoms can be analyzed by the inert gas melting-infrared absorption method.

From the viewpoint of dispersion stability and light-shielding property, the specific surface area of the titanium nitride-containing particles ^{is preferably 5 m 2} / g or more and 100 m ² / g or less, and ^{more preferably 10 m 2} / g or more and 60 m ² / g or less. The specific surface area can be determined by the BET (Brunauer, Emmett, Teller) method.

The titanium nitride-containing particles may be composite fine particles composed of titanium nitride particles and metal fine particles.
The composite fine particles are particles in which titanium nitride particles and metal fine particles are composited or highly dispersed. Here, "composite" means that the particles are composed of both titanium nitride and metal components, and "highly dispersed state" means that the titanium nitride particles and the metal particles are present. It means that the particles exist individually and the particles of a small amount of components are uniformly and uniformly dispersed without agglomeration.
The metal fine particles are not particularly limited, and for example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium, and bismuth. , Antimon and lead, and at least one of these alloys. Among them, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and at least one selected from these alloys are preferable, and copper, silver, gold, platinum and tin, and these. It is more preferable that it is at least one selected from the alloys of. From the viewpoint of being more excellent in moisture resistance, silver is preferable.
The content of the metal fine particles in the titanium nitride-containing particles is preferably 5% by mass or more and 50% by mass or less, and 10% by mass or more and 30% by mass or less with respect to the total mass of the titanium nitride-containing particles. Is more preferable.

-Peak diffraction angle 2θ of titanium nitride-containing particles
The titanium nitride-containing particles preferably have a diffraction angle 2θ of a peak derived from the (200) plane when CuKα ray is used as an X-ray source, which is more than 42.6 ° and 43.5 ° or less. A cured film (for example, a black matrix) obtained by using a curable composition containing titanium nitride-containing particles having such characteristics can achieve a high OD value.

When the X-ray diffraction spectrum of a titanium compound is measured using CuKα ray as an X-ray source, the peak derived from the (200) plane of TiN is close to 2θ = 42.5 ° as the peak with the strongest intensity, and TiO is (200). ) A peak derived from the plane is observed near 2θ = 43.4 °. On the other hand, most peaks not strength strong peak is anatase TiO ₂ is derived from the (200) plane in the vicinity 2 [Theta] = 48.1 °, rutile TiO ₂ and a peak derived from (200) plane is 2 [Theta] = 39 It is observed near 2 °. Therefore, the more the crystal state contains a large amount of oxygen atoms, the more the peak position shifts to the higher angle side with respect to 42.5 °.

The diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.6 ° and less than 43.5 ° from the viewpoint of the temporal stability of the particles, and further, during production. From the viewpoint of excellent process margin, 42.7 ° or more and less than 43.5 ° is more preferable, and from the viewpoint of excellent reproducibility of particle performance, 42.7 ° or more and less than 43.4 ° is further preferable. _{When titanium oxide TiO 2} is contained as a sub-component, _{the peak derived from anatase-type TiO 2} (101) is close to 2θ = 25.3 ° as the strongest peak, _{and the peak derived from rutile-type TiO 2} (110) is present. Is found near 2θ = 27.4 °. However, since TiO ₂ is white and causes a factor of lowering the light-shielding property of the black matrix, it is preferable that it is reduced to such an extent that it is not observed as a peak.

The crystallite size constituting the titanium nitride-containing particles can be obtained from the half width of the X-ray diffraction peak, and is calculated using Scheller's formula.

The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm. By forming a black matrix using titanium nitride-containing particles having a crystallite size of 20 nm or more, the transmitted light of the cured film exhibits a blue to bluish purple color such that its peak wavelength is 475 nm or less, and has high light-shielding properties. A black matrix having both ultraviolet sensitivity can be obtained. When the crystallite size is 20 nm or more, the ratio of the active particle surface to the particle volume becomes small and a good balance is obtained, and the heat resistance and / or durability of the titanium nitride-containing particles is more excellent. It becomes.

(Metal Nitride-Containing Particles Containing Atom A)
As the inorganic pigment, metal nitride-containing particles which are metal nitride-containing particles and which contain a predetermined atom A in the metal nitride-containing particles can also be used.
Examples of the metal in the metal nitride-containing particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re, and the curable composition is more excellent in the effect of the present invention. Nb or V is more preferable in that it has.
Examples of the atom A include B, Al, Si, Mn, Fe, Ni, Ag and the like.
When the metal nitride-containing particles contain the atom A, the content thereof is not particularly limited, but the content of the atom A in the metal nitride-containing particles is preferably 0.00005 to 10% by mass.

The method for producing the metal nitride-containing particles containing the atom A is not particularly limited, and a known method can be used.
The vapor phase reaction method is usually used for producing the metal nitride-containing particles, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because of the fact that impurities are less mixed, the particle size is easily uniform, and the productivity is high.
Specific examples of the method for producing metal nitride-containing particles by the thermal plasma method include those using a metal fine particle production apparatus (an apparatus similar to the “black composite fine particle production apparatus” described later). The metal fine particle manufacturing apparatus includes, for example, a plasma torch that generates thermal plasma, a material supply apparatus that supplies metal raw material powder into the plasma torch, a chamber that includes a cooling function, a cyclone that classifies the generated metal fine particles, and metal fine particles. It is composed of a collection unit that collects the particles.
In the present specification, the metal fine particles are intended to be particles containing a metal element and having a primary particle diameter of 20 nm to 40 μm.

The method for producing the metal nitride-containing particles using the metal fine particle producing apparatus is not particularly limited, and a known method can be used. Above all, the method for producing metal nitride-containing particles using the metal fine particle production apparatus may include the following steps in that the yield of the metal nitride-containing particles having the following predetermined average primary particle diameter is increased. preferable.
Step A: A step of supplying an inert gas containing no nitrogen gas into the plasma torch as plasma gas to generate a thermal plasma flame.
Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
Step C: A step of cooling the raw material metal of the gas phase to obtain metal fine particles containing a transition metal.
Step D: A step of supplying an inert gas containing nitrogen gas into the plasma torch as plasma gas to generate a thermal plasma flame.
Step E: A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a raw metal for a gas phase.
Step F: A step of cooling the raw material metal of the gas phase to obtain metal nitride-containing particles.
Further, the method for producing the metal nitride-containing particles may include the following step G, if desired, after the above steps C and / or step F.
Step G: A step of classifying the obtained particles.
Further, the following step A2 may be contained before step A, between step A and step B, between step C and step D, or between step D and step E.
Step A2: A step of mixing the atom A with the metal raw material powder containing the transition metal.
Further, the following steps A3-1 to A3-3 may be included before the step A2.
Step A3-1: A step of supplying an inert gas containing no nitrogen gas into the plasma torch as plasma gas to generate a thermal plasma flame.
Step A3-2: A step of supplying a raw material powder containing an atom A to a thermal plasma flame in a plasma torch and evaporating the raw material powder to obtain a gas phase atom A.
Step A3-3: A step of cooling the atom A in the gas phase to obtain atomized atom A.
In addition, step G may be further contained after step A3-3.
In the present specification, the atomized atom A is intended to be a particle containing the atom A and having a primary particle diameter of 20 nm to 40 μm.

Further, the method for producing the metal nitride-containing particles preferably further contains the following step H after the step F (when the step G is contained, after the step G after the step F).
Step H: A step of exposing the metal nitride-containing particles obtained in Step F (or Step G) to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
If desired, the method for producing the metal nitride-containing particles may further include step G after step H. Hereinafter, preferred embodiments of each step will be described in detail.

・ Process A
Step A is a step of supplying an inert gas containing no nitrogen gas into the plasma torch as plasma gas to generate a thermal plasma flame. The method for generating the thermal plasma flame is not particularly limited, and examples thereof include a DC arc discharge method, a multiphase arc discharge method, a high frequency plasma method, a hybrid plasma method, and the high frequency plasma method in which impurities are less mixed from the electrodes. preferable.
The method for generating a thermal plasma flame by the high-frequency plasma method is not particularly limited. For example, plasma gas is supplied into a plasma torch containing a high-frequency oscillation coil and a quartz tube, and a high-frequency current is applied to the high-frequency oscillation coil. A method of obtaining a thermal plasma flame by doing so can be mentioned.
Examples of the plasma gas in the step A include an inert gas that does not contain nitrogen gas. Examples of the inert gas that does not contain nitrogen gas include argon gas, hydrogen gas, and the like. As the inert gas containing no nitrogen gas, one type may be used alone or two or more types may be used in combination.

・ Process A2
Step A2 is a step of mixing the atom A with the metal raw material powder containing the transition metal. The method for mixing the raw metal powder and the atom A is not particularly limited, and a known method can be used. For example, the material supply device for supplying the metal raw material powder into the plasma torch may include a mixing and dispersing function. Specifically, the material supply apparatus described in paragraphs 0047 to 0058 of International Publication No. 2010/147098 can be used, the contents of which are incorporated herein by reference. The method for producing the metal nitride-containing particles may further contain the following steps A3-1 to A3-3 before the step A2.

・ Process B
Step B is a step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal. The method of supplying the metal raw material powder to the thermal plasma flame in the plasma torch is not particularly limited, but the raw metal of the obtained gas phase may be sprayed using a carrier gas in that the raw metal of the vapor phase becomes more uniform. preferable. As the carrier gas, it is preferable to use an inert gas that does not contain nitrogen gas. The embodiment of the inert gas that does not contain nitrogen gas is as described above.
When the method for producing the metal nitride-containing particles contains the above step A2, the metal raw material powder is maintained in a uniform dispersed state until the metal raw material powder is supplied into the plasma torch. Is preferable.

・ Process C
Step C is a step of cooling the raw material metal of the gas phase to obtain metal fine particles containing a transition metal. The cooling method is not particularly limited, but it is preferable to use a chamber containing a cooling function. By introducing the raw material metal of the gas phase obtained in step B into a chamber containing the cooling function and quenching in the chamber, the following metal fine particles having a desired particle size can be produced. The generated metal fine particles are recovered by, for example, a recovery unit. As the atmosphere in the chamber, an inert gas containing no nitrogen gas is preferable. The embodiment of the inert gas that does not contain nitrogen gas is as described above.
By going through the above steps A to C, metal fine particles containing a transition metal can be obtained. The metal fine particles containing the transition metal are likely to evaporate in step E. Even when the metal raw material powder contains impurities, the impurities can be removed by going through the steps A to C.

・ Process D
Step D is a step of supplying an inert gas containing nitrogen gas into the plasma torch as plasma gas to generate a thermal plasma flame. Examples of the nitrogen-containing inert gas include nitrogen gas and nitrogen gas containing an inert gas. Examples of the inert gas include argon gas, hydrogen gas and the like. The nitrogen gas containing the inert gas is not particularly limited, but the content of the nitrogen gas is usually about 10 to 90 mol%, preferably about 30 to 60 mol%. Other aspects are the same as in step A.

・ Process E
Step E is a step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a raw metal for a gas phase. The method for supplying the metal fine particles to the thermal plasma flame in the plasma torch is as described above, but the carrier gas is preferably an inert gas containing nitrogen. The aspects of the inert gas containing nitrogen are as described above.
In step E, since the raw metal that has become metal fine particles in steps A to C is supplied to the thermal plasma flame, the raw metal of the gas phase is likely to be obtained, and the state of the raw metal of the gas phase is likely to be more uniform.

・ Process F
Step F is a step of cooling the raw material metal of the gas phase to obtain metal nitride-containing particles containing the nitride of the transition metal. The preferred embodiment of the cooling method is as described above, but the atmosphere in the chamber is preferably an inert gas containing nitrogen gas. A preferred embodiment of the inert gas containing nitrogen gas is as described above.

・ Process G
Step G is a step of classifying the obtained metal fine particles and / or metal nitride-containing particles. The classification method is not particularly limited, and for example, a cyclone can be used. The cyclone has a container on a cone, generates a swirling flow in the container, and has a function of classifying particles by utilizing centrifugal force. The classification is preferably performed in an atmosphere of an inert gas. The aspects of the inert gas are as described above.

・ Process H
Step H is a step of exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment. By going through this step, the content of the metal nitride in the metal nitride-containing particles can be increased. The method of exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen gas is not particularly limited. For example, the metal nitride-containing particles are introduced into a constant temperature bath filled with a gas mixed with water vapor and nitrogen gas. , A method of allowing or stirring for a predetermined time is mentioned, and it is more preferable to allow the metal nitride-containing particles to stand at a point where the surface and the crystal boundary are more stabilized.
The mixing ratio of water vapor and nitrogen gas is preferably a condition in which the relative humidity is 25 to 95% in the atmosphere. The time for standing or stirring is preferably 0.5 to 72 hours, and the temperature at that time is preferably 10 to 40 ° C.

-Steps A3-1 to A3-3
In steps A3-1 to A3-3, an inert gas containing no nitrogen gas is supplied as plasma gas into the plasma torch to generate a thermal plasma flame (A3-1), which is used for the thermal plasma flame in the plasma torch. , The step of supplying the raw material powder containing the atom A and evaporating the raw material powder to obtain the atom A of the gas phase (A3-2), and cooling the atom A of the gas phase to obtain fine particles composed of the atom A. This is the obtaining step (A3-3). Aspects in each step are the above-mentioned step A, step B (using a raw material powder containing an atom A instead of the metal raw material powder containing a transition metal), and step C (instead of metal fine particles containing a transition metal). The atom A is obtained as fine particles.).
By going through the above steps, the atoms A are made into fine particles, and the atoms A are easily evaporated in the step E. Further, by going through the above steps, impurities (metal components other than atom A, etc.) contained in the raw material powder containing atom A can be removed.

-Preferable Mode of Method for Producing Metal Nitride-Containing Particles Containing Atom A As a preferred embodiment of the method for producing metal nitride-containing particles containing atom A, a method having the following steps in order can be mentioned.
-Step A: A step of supplying an inert gas containing no nitrogen gas into the plasma torch as plasma gas to generate a thermal plasma flame.
Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
-Step C: A step of cooling the raw material metal of the gas phase to obtain metal fine particles containing a transition metal.
-Step G: A step of classifying the obtained particles.
-Step A3-1: A step of supplying an inert gas containing no nitrogen gas into the plasma torch as plasma gas to generate a thermal plasma flame.-Step A3-2: Atom A is added to the thermal plasma flame in the plasma torch. Step / Step A3-3: A step / step of supplying the contained raw material powder and evaporating the raw material powder to obtain a gas phase atom A 3-3: A step / step of cooling the gas phase atom A to obtain a finely divided atom A. G: A step of classifying the obtained particles.
Step A2: A step of mixing an atom A (in this case, atomized A) with a metal raw material powder containing a transition metal (in this case, metal fine particles).
-Step D: A step of supplying an inert gas containing nitrogen gas into a plasma torch as plasma gas to generate a thermal plasma flame.
Step E: A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a raw metal for a gas phase.
-Step F: A step of cooling the raw material metal of the gas phase to obtain metal nitride-containing particles.
-Step G: A step of classifying the obtained particles.
Step H: A step of exposing the metal nitride-containing particles obtained in Step G to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
In the above series of steps, the order of steps A to C and steps A3-1 to A3-3 may be changed. That is, steps A to C may be carried out after steps A3-1 to A3-3.

According to the preferred embodiment of the method for producing metal nitride-containing particles containing atom A, the metal raw material powder and the metal nitride having a desired average primary particle size while being able to remove impurities contained in the raw material particles. Containing particles can be produced. The reason is that the transition metal and / or atom A is ionized by plasma treatment, and when the ion is cooled, the transition metal, atom A and impurities are atomized reflecting their respective melting points. It is presumed. At this time, the atom having a low melting point has a high particle formation, and the atom having a high melting point has a slow particle formation. Therefore, as described above, it is presumed that the fine particles (steps B and C, and steps A3-2 and A3-3) once plasma-treated tend to become a single component (single crystal). By classifying the single component particles obtained as described above, the impurity particles can be removed depending on the difference in density and / or particle size between the transition metal particles and / or the atom A particles and the impurity particles. it can. The above classification can be performed by appropriately setting the classification conditions using, for example, a cyclone or the like.

-Metal Raw Material Powder and Purification of Raw Material Powder A metal raw material powder containing a transition metal that can be used in the above step B (hereinafter, simply referred to as "metal raw material powder") and a raw material powder containing an atom A (hereinafter, simply "" The "raw material powder") is not particularly limited, but is preferably of high purity. The content of the transition metal in the metal raw material powder is not particularly limited, but is preferably 99.99% or more, and more preferably 99.999% or more. The same applies to the content of atom A in the raw material powder.

The metal raw material powder and / or the raw material powder may contain an atom other than the desired transition metal and / or atom A as an impurity. Examples of impurities contained in the metal raw material powder include boron, aluminum, silicon, manganese, iron, nickel and silver. Examples of impurities contained in the raw material powder include metal elements and the like.

In the method for producing the metal nitride-containing particles, the following step A0 may be further contained before the step B (when the step A2 is contained, before the step A2).
Step A0: A step of removing impurities from the metal raw material powder and / or the raw material powder.

・ Process A0
In step A0, the method for removing impurities from the metal raw material powder and / or the raw material powder (separation and purification method) is not particularly limited, and for example, Niob is described in paragraphs 0013 to 0030 of JP2012-211048A. A method can be used, and a similar method can be used for other metal raw material powders and / or raw material powders.

-Coating of Metal Nitride-Containing Particles The metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, it may be a coated metal nitride-containing particle having a metal nitride-containing particle and a coating layer formed by using an inorganic compound that coats the metal nitride-containing particle. Curable compositions containing metal nitride-containing particles coated with an inorganic compound have better dispersion stability.
The inorganic compound is not particularly limited, and oxides such as SiO ₂ , ZrO ₂ , TiO ₂ , GeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , and P ₂ O ₅ , as well as aluminum hydroxide and zirconium hydride. Hydroxides such as. Of these, aluminum hydroxide is preferable because it is easy to form a thinner film and a film having a higher coverage.
When it is intended to control the refractive index of the metal nitride-containing particles, silicon oxide is preferable as the low refractive index film, and zirconium hydride is preferable as the high refractive index film.
The method for coating the metal nitride-containing particles with the inorganic compound is not particularly limited, but it is preferable that the method for producing the metal nitride-containing particles includes the following inorganic compound coating step.

-Inorganic compound coating step The inorganic compound coating step is a step of coating the above-mentioned metal nitride-containing particles with an oxide and / or a hydroxide. The coating method is not particularly limited, and examples thereof include the following wet coating methods.

As the first wet coating method, first, the above-mentioned metal nitride-containing particles are mixed with water to prepare a slurry. Next, the above slurry is reacted with a water-soluble compound (for example, sodium silicate) containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y, and P, and an excess is added. Remove the alkali ions with decantation and / or ion exchange resin or the like. Then, the slurry is dried to obtain oxide-coated metal nitride-containing particles.

As the second wet coating method, first, the above-mentioned metal nitride-containing particles are mixed with an organic solvent such as alcohol to prepare a slurry. Next, an organometallic compound such as an alkoxide containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y, and P is produced in the slurry, and the slurry is heated at a high temperature. Bake. When the slurry is calcined at a high temperature, the sol-gel reaction proceeds to obtain metal nitride-containing particles coated with an oxide.

As a third wet coating method, a slurry containing an ionic liquid is prepared using urea and aluminum chloride in the presence of metal nitride-containing particles. The metal nitride-containing particles are taken out from this slurry, dried, and then calcined to obtain the metal nitride-containing particles coated with a hydroxide containing aluminum hydroxide.

(Organic pigment)
Examples of organic pigments include Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24. , 31, 32, 34, 35, 35: 1,36, 36: 1,37, 37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77 , 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 , 126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171 , 172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc .;
C. I. Pigment Orange 2,5,13,16,17: 1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73, etc. ;
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4, 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279, etc.;
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment Violet 1,19,23,27,32,37,42, etc .; and C.I. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,60,64,66,79,80, etc .;
Can be mentioned. The pigment may be used alone or in combination of two or more.

<Dye>
Examples of the dye include JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A-2592207, and US Pat. No. 4,808.501. , U.S. Pat. No. 5,667,920, U.S. Patent No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. You can use the dyes that are used. When classified by chemical structure, pyrazole azo compound, pyromethene compound, anilino azo compound, triphenylmethane compound, anthraquinone compound, benzylidene compound, oxonor compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyropyrazole azomethin compound, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097. A polymerizable dye having an intramolecular polymerizable dye may be used, and examples of commercially available products include the RDW series manufactured by Wako Pure Chemical Industries, Ltd.

<Infrared absorber>
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in a wavelength region in the infrared region (preferably, a wavelength of 650 to 1,300 nm). Preferably, the infrared absorber is a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm.
Examples of the colorant having such spectral characteristics include a pyrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an iminium compound, a thiol complex compound, a transition metal oxide compound, a squarylium compound, a naphthalocyanine compound, and a quoterylene. Examples thereof include compounds, dithiol metal complex compounds, croconium compounds and the like.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750 may be used, and the contents thereof are described in the present specification. Be incorporated. For the cyanine compound, for example, "functional dye, Shin Ogawara / Ken Matsuoka / Eijiro Kitao / Tsuneaki Hirashima, Kodansha Scientific" can be referred to, and this content is incorporated in the present specification.

Examples of the colorant having the above spectral characteristics include a compound disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or a compound disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP-A-2011-164583. Near-infrared absorbing particles composed of crystallites of oxides containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication and having a number average aggregate particle size of 5 to 200 nm can also be used.

As the compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm, at least one selected from the group consisting of a cyanine compound, a pyrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound is preferable.
The infrared absorber is preferably a compound that dissolves in water at 25 ° C. in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25 ° C. in an amount of 10% by mass or more. By using such a compound, the solvent resistance is improved.
For the pyrrolopyrrole compound, paragraphs 0049 to 0062 of JP-A-2010-222557 can be referred to, and the contents thereof are incorporated in the present specification. Cyanine compounds and squarylium compounds are described in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraph numbers 0053 to 0118 of International Publication No. 2014/03628, paragraph numbers 0028 to 0074 of JP2014-59550A, and international publication. Publication No. 2012/169447, paragraph numbers 0013 to 0091, Japanese Patent Application Laid-Open No. 2015-176046, paragraph numbers 0019 to 0033, Japanese Patent Application Laid-Open No. 2014-63144, paragraph numbers 0053 to 0999, Japanese Patent Application Laid-Open No. 2014-52431 Nos. 008-5150, paragraphs 0076 to 0124 of JP2014-444301, paragraphs 0045 to 0078 of JP2012-8532, paragraphs 0027 to 0067 of JP2015-172102, JP2015 -172004, paragraph numbers 0029 to 0067, Japanese Patent Application Laid-Open No. 2015-40895, paragraph numbers 0029 to 0085, Japanese Patent Application Laid-Open No. 2014-126642, paragraph numbers 0022 to 0036, Japanese Patent Application Laid-Open No. 2014-148567, paragraph numbers 0011. ~ 0017, Paragraph numbers 0010 to 0025 of JP2015-157893, Paragraphs 0013 to 0026 of JP2014-095007, Paragraphs 0013 to 0047 of JP2014-80487, and JP2013-2013. Paragraphs 0007 to 0028 and the like of Japanese Patent Application Laid-Open No. 227403 can be referred to, and the contents thereof are incorporated in this specification.

一般式１中、Ａ¹およびＡ²はそれぞれ独立にアリール基、ヘテロアリール基又は下記一般式１−Ａで表される基を表す。
一般式１−Ａ

一般式１−Ａ中、Ｚ^1Aは含窒素複素環を形成する非金属原子団を表し、Ｒ^2Aはアルキル基、アルケニル基、又はアラルキル基を表し、ｄは０又は１を表し、波線は連結手を表す。
一般式２

一般式２中、Ｒ^1aおよびＲ^1bはそれぞれ独立にアルキル基、アリール基、又はヘテロアリール基を表し、
Ｒ²〜Ｒ⁵はそれぞれ独立に水素原子、又は置換基を表し、Ｒ²とＲ³、Ｒ⁴とＲ⁵は、それぞれ結合して環を形成していてもよく、
Ｒ⁶及びＲ⁷はそれぞれ独立に水素原子、アルキル基、アリール基、ヘテロアリール基、−ＢＲ^AＲ^B、又は金属原子を表し、Ｒ^A及びＲ^Bはそれぞれ独立に水素原子、又は置換基を表し、
Ｒ⁶は、Ｒ^1a又はＲ³と、共有結合又は配位結合していてもよく、
Ｒ⁷は、Ｒ^1b又はＲ⁵と、共有結合又は配位結合していてもよい。
一般式３

一般式３中、Ｚ¹及びＺ²はそれぞれ独立に縮環してもよい５員、又は６員の含窒素複素環を形成する非金属原子団であり、
Ｒ¹⁰¹及びＲ¹⁰²はそれぞれ独立にアルキル基、アルケニル基、アルキニル基、アラルキル基、又はアリール基を表し、
Ｌ¹は奇数個のメチンからなるメチン鎖を表し、
ａ及びｂはそれぞれ独立に０又は１であり、
ａが０の場合は、炭素原子と窒素原子とが二重結合で結合し、ｂが０の場合は、炭素原子と窒素原子とが単結合で結合し、
式中のＣｙで表される部位がカチオン部である場合、Ｘ¹はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ¹はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。The infrared absorber is preferably at least one selected from the group consisting of the compounds represented by the following general formulas 1 to 3.
General formula 1

In the general formula 1, A ¹ and A ² independently represent an aryl group, a heteroaryl group, or a group represented by the following general formula 1-A, respectively.
General formula 1-A

In the general formula 1-A, Z ^1A represents a non-metal atomic group forming a nitrogen-containing heterocycle, R ^2A represents an alkyl group, an alkenyl group, or an aralkyl group, d represents 0 or 1, and wavy lines are connected. Represent a hand.
General formula 2

In General Formula 2, R ^1a and R ^1b independently represent an alkyl group, an aryl group, or a heteroaryl group, respectively.
R ^{2 to} R ⁵ independently represent a hydrogen atom or a substituent, and R ² and R ³ and R ⁴ and R ⁵ may be bonded to each other to form a ring.
R ⁶ and R ⁷ are independently a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^A R ^B, or represents a metal atom, R ^A and R ^B are each independently a hydrogen atom, or a substituent Represent,
R ⁶ may be covalently or coordinated with ^{R 1a} or R ^3.
R ⁷ may be covalently or coordinated with ^{R 1b} or R ^5.
General formula 3

In the general formula 3, Z ¹ and Z ² are non-metal atomic groups forming a 5- or 6-membered nitrogen-containing heterocycle which may be independently fused.
R ¹⁰¹ and R ¹⁰² independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group, respectively.
L ¹ represents a methine chain consisting of an odd number of methines.
a and b are independently 0 or 1, respectively.
When a is 0, the carbon atom and the nitrogen atom are bonded by a double bond, and when b is 0, the carbon atom and the nitrogen atom are bonded by a single bond.
When the part represented by Cy in the formula is a cation part, X ¹ represents an anion, c represents the number required to balance the charges, and the part represented by Cy in the formula is an anion part. When, X ¹ represents a cation, c represents the number required to balance the charge, and c is intramolecularly neutralized when the charge at the site represented by Cy in the equation is neutralized. It is 0.

<Pigment derivative>
The curable composition may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is replaced with an acidic group, a basic group or a phthalimide methyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferable from the viewpoint of dispersibility and dispersion stability of the colorant A. The pigment derivative is particularly preferably having a basic group. The combination of the resin (dispersant) and the pigment derivative described above is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.

Organic pigments for constituting pigment derivatives include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, and thioindigo pigments. , Isoindrin-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, slene-based pigments, metal complex-based pigments and the like.
As the acidic group contained in the pigment derivative, a sulfonic acid group, a carboxylic acid group and a salt thereof are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is further preferable. As the basic group contained in the pigment derivative, an amino group is preferable, and a tertiary amino group is more preferable.

When the curable composition contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the mass of the pigment. Only one kind of pigment derivative may be used, or two or more kinds may be used in combination.

[Photopolymerization initiator]
The photopolymerization initiator is not particularly limited as long as it can initiate the polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, one having photosensitivity from the ultraviolet region to the visible light region is preferable. Further, it may be an activator that causes some action with a photoexcited sensitizer to generate an active radical, or may be an initiator that initiates cationic polymerization depending on the type of the polymerizable compound.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in a wavelength region of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, based on the total solid content of the curable composition. More than mass% is particularly preferable, 30% by mass or less is preferable, 20% by mass or less is more preferable, 10% by mass or less is further preferable, and less than 10% by mass is particularly preferable.
When the content of the photopolymerization initiator is more than 1% by mass and less than 10% by mass with respect to the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination. When two or more kinds of photopolymerization initiators are used in combination, the total amount thereof is preferably within the above range.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and the like. Examples thereof include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, and hydroxyacetophenone.
Examples of the halogenated hydrocarbon compound containing the triazine skeleton include Wakabayashi et al., Bull. Chem. Soc. Japanese Patent No. 42, 2924 (1969), British Patent No. 1388492, Compound described in JP-A-53-133428, German Patent No. 3337024, F.I. C. J. by Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-58241, compound described in JP-A-5-281728, compound described in JP-A-5-341920, US Pat. No. 4,212,976. Examples include the compounds described in the book.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, A compound selected from the group consisting of a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxaziazole compound, and a 3-aryl substituted coumarin compound is preferable.

Of these, trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, or acetophenone compounds are more preferable, and trihalomethyltriazine compounds and α- At least one compound selected from the group consisting of an aminoketone compound, an oxime compound, a triallyl imidazole dimer, and a benzophenone compound is more preferable.

In particular, when the curable composition is used for producing a light-shielding film, it is necessary to form a fine pattern in a sharp shape, so it is important to develop the curable composition without any residue in the unexposed portion. is there. From this point of view, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when forming a fine pattern, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Considering these points, it is particularly preferable to use an oxime compound as the photopolymerization initiator in order to form a fine pattern.
As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF) can be used.
As the aminoacetophenone compound, commercially available products IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names, all manufactured by BASF) can be used. As the aminoacetophenone compound, the compound described in JP-A-2009-191179, in which the absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm, can also be used.
As the acylphosphine compound, commercially available IRGACURE-819 or DAROCUR-TPO (trade name, both manufactured by BASF) can be used.

<Oxime compound>
The photopolymerization initiator is more preferably an oxime compound (oxime-based initiator). In particular, the oxime compound is preferable because it has high sensitivity and high polymerization efficiency, can cure the curable composition layer regardless of the colorant concentration, and has a high colorant concentration and is easy to design.
As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, or the compound described in JP-A-2006-342166 can be used.
Examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyminobtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyl Examples thereof include oxyimino-1-phenylpropan-1-one.
In addition, J. C. S. Perkin II (1979) pp. 1653-1660), J. Mol. C. S. Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, the compounds described in JP-A-2000-66385, the compounds described in JP-A-2000-80068, JP-A-2004-534977, and JP-A-2006-342166 are also mentioned. ..
As commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) are also preferably used. In addition, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA), or N-1919 (carbazole / oxime ester skeleton-containing light start) An agent (manufactured by ADEKA Corporation)) can also be used.

As an oxime compound other than the above, the compound described in JP-A-2009-5199004 in which an oxime is linked to the N-position of carbazole; the compound described in US Pat. No. 7,626,957 in which a heterosubstituted group is introduced at a benzophenone moiety; Compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at a site; ketooxime compounds described in International Publication Patent No. 2009-131189; the same molecule as a triazine skeleton and an oxime skeleton. The compound described in Japanese Patent Application Laid-Open No. 7556910; the compound described in Japanese Patent Application Laid-Open No. 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source; and the like may be used. ..
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, the contents of which are incorporated herein by reference.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. It should be noted that the NO bond of the oxime compound may be the (E) -form oxime compound, the (Z) -form oxime compound, or a mixture of the (E) -form and the (Z) -form. Good.

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.
Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group and the like. These groups may have one or more substituents. Moreover, the above-mentioned substituent may be further substituted with another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group and the like.
In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.
In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.

An oxime compound containing a fluorine atom can also be used as the photopolymerization initiator. Specific examples of the oxime compound containing a fluorine atom include compounds described in JP-A-2010-262028; compounds 24, 36-40 described in JP-A-2014-500852; compounds described in JP-A-2013-164471. (C-3); and the like. This content is incorporated herein by reference.

As the photopolymerization initiator, compounds represented by the following general formulas (1) to (4) can also be used.

In the formula (1), R ¹ and R ² are independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Representing an arylalkyl group having 7 to 30 carbon atoms, when R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are independent of each other. It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond or a carbonyl group. Indicates a group.

In the formula ^(2), R ^1, R 2, ^{R 3} and ^{R 4} have the same meanings as ^{R 1,} R 2, ^{R 3} and ^{R 4} in Formula (1), ^{R 5 is} -R 6, -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSO R ⁶ , -CN, Halogen Represents an atom or a hydroxyl group, and R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. X represents a direct bond or a carbonyl group, and a represents an integer from 0 to 4.

In the formula (3), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. Representing an alkyl group, R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or 4 carbon atoms, respectively. Represents a heterocyclic group of ~ 20, where X represents a direct bond or a carbonyl group.

In the formula ^(4), R 1, ^{R 3} and ^{R 4} have the same meanings as ^R 1, ^{R 3} and ^{R 4} in the formula ^(3), R ^{5 is, -R 6, -OR 6, -SR} 6, Represents -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ^{6 , -SCOR 6} , -OCSR ⁶ , -COSR ⁶ , -COR ⁶ , -CN, halogen atom or hydroxyl group. R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryl alkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a heterocyclic group having 4 to 20 carbon atoms. It represents a carbonyl group, where a represents an integer from 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group, respectively. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a trill group or a xsilyl group. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. Direct binding is preferable for X.
In the above formulas (3) and (4), R ¹ is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group, respectively. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xsilyl group. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. Direct binding is preferable for X.
Specific examples of the compounds represented by the formulas (1) and (2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein by reference.

Specific examples of the oxime compound preferably used in the curable composition are shown below.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and further preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, from the viewpoint of sensitivity, 5,000 to 200, It is more preferably 000.
A known method can be used for the molar extinction coefficient of the compound. For example, an ultraviolet-visible spectrophotometer (Varian Cary-5 spctrophotometer) is used with an ethyl acetate solvent at a concentration of 0.01 g / L. It is preferable to measure.
Two or more kinds of photopolymerization initiators may be used in combination, if necessary.

[Polymerizable compound]
The curable composition contains a polymerizable compound.
The content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the curable composition. The lower limit is, for example, 1.0% by mass or more, more preferably 3.5% by mass or more, and particularly preferably more than 3.5% by mass. The upper limit is, for example, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably less than 20% by mass.
When the content of the polymerizable compound is more than 3.5% by mass and less than 20% by mass with respect to the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent. ..
As the polymerizable compound, one type may be used alone, or two or more types may be used in combination. When two or more kinds of polymerizable compounds are used in combination, the total amount thereof is preferably within the above range.

The polymerizable compound is preferably a compound containing one or more groups containing an ethylenically unsaturated bond, more preferably two or more, further preferably three or more, and five or more. Is particularly preferable. The upper limit is, for example, 15 or less. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof, and a monomer is preferable.
The molecular weight of the polymerizable compound is preferably 100 to 3,000, more preferably 250 to 1,500.
The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides, and multimers thereof. These are preferably esters of unsaturated carboxylic acids and aliphatic polyvalent alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide containing a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, and the above-mentioned non-functional group. A dehydration condensation reaction product of a saturated carboxylic acid ester or amide and a monofunctional or polyfunctional carboxylic acid is also preferably used. Further, a reaction product of an unsaturated carboxylic acid ester or amide containing an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, or a halogen group. Alternatively, a reaction product of an unsaturated carboxylic acid ester or amide containing a desorbing substituent such as a tosyloxy group with a monofunctional or polyfunctional alcohol, amines or thiols is also suitable. Further, instead of the unsaturated carboxylic acid described above, a compound group in which a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like is replaced can be used.
As these specific compounds, the compounds described in paragraphs 0995 to 0108 of JP2009-288705A can be preferably used in the present invention as well.

The polymerizable compound is also preferably a compound having one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure. For example, the compounds described in paragraphs 0227 of JP2013-29760A and paragraphs 0254 to 0257 of JP2008-292970 can be referred to, and the contents thereof are incorporated in the present specification.

The polymerizable compounds are dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), and di. Pentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-) 12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues (for example, SR454, SR499 commercially available from Sartmer) are preferable. These oligomer types can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.
The preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound. A polymerizable compound having an acid group is more preferable, and in this ester, those in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol are further preferable. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

The preferable acid value of the polymerizable compound containing an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing and dissolving properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Further, within the above range, the photopolymerization performance is good and the curability is excellent.

As the polymerizable compound, a compound containing a caprolactone structure is also a preferable embodiment.
The compound containing a caprolactone structure is not particularly limited as long as the caprolactone structure is contained in the molecule, and for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, dimethylolpropane, pentaerythritol, and dipenta are used. Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohols such as erythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. Can be mentioned. Of these, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.

In the formula (Z-1), all 6 Rs are groups represented by the following formula (Z-2), or 1 to 5 of the 6 Rs are the following formulas (Z-2). It is a group represented by, and the residue is a group represented by the following formula (Z-3).

In formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and * represents a bond.

In formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and * represents a bond.

The polymerizable compound containing a caprolactone structure is commercially available, for example, from Nippon Kayaku as the KAYARAD DPCA series, in which m is 1 in formulas (Z-1) to (Z-3) and formula (Z-). The number of groups represented by 2) is 2, the number of groups represented by R ¹ is all hydrogen atoms), DPCA-30 (in the same formula, m is 1, and the number of groups represented by formula (Z-2) is 3. , R ¹ is a compound in which all hydrogen atoms are present), DPCA-60 (in the same formula, m is 1, the number of groups represented by the formula (Z-2) is 6, and R ¹ is a compound in which all hydrogen atoms are present). , DPCA-120 (a compound in which m is 2 in the same formula, the number of groups represented by the formula (Z-2) is 6, and R ¹ is a hydrogen atom) and the like.

As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can also be used.

In formulas (Z-4) and (Z-5), E independently produces − ((CH ₂ ) _y CH ₂ O) − or ((CH ₂ ) _y CH (CH ₃ ) O) −. Representing y, each independently represents an integer of 0 to 10, and X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each of m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each of n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.
_{-((CH 2} ) _y CH ₂ O)-or ((CH ₂ ) _y CH (CH ₃ ) O)-in the formula (Z-4) or the formula (Z-5) has the terminal on the oxygen atom side. The form that binds to X is preferable.

The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. In particular, among the forms in which all 6 Xs are acryloyl groups in the formula (Z-5), the compounds in which all 6 Xs are acryloyl groups in the formula (Z-5), and the 6 Xs. An embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a configuration, the developability can be further improved.

The total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more.

The compound represented by the formula (Z-4) or the formula (Z-5) is obtained by ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known step. It can be synthesized from a step of binding a ring-opening skeleton and a step of reacting, for example, (meth) acryloyl chloride with a terminal hydroxy group of the ring-opening skeleton to introduce a (meth) acryloyl group. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the formula (Z-4) or the formula (Z-5), the pentaerythritol derivative and / or the dipentaerythritol derivative is more preferable.
Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as "exemplified compounds (a) to (f)"), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferable.

Commercially available products of the polymerizable compounds represented by the formulas (Z-4) and (Z-5) include SR-494, which is a tetrafunctional acrylate containing four ethyleneoxy chains manufactured by Sartmer, and Nippon Kayaku. Examples thereof include DPCA-60, which is a hexafunctional acrylate containing 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate containing 3 isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-Open No. 2-16765; Urethane compounds containing an ethylene oxide-based skeleton described in Japanese Patent Publication No. 49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418; are also suitable. Further, an addition-polymerizable compound having an amino structure and / or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. By using the above, a curable composition having a very excellent photosensitive speed can be obtained.
Commercially available products include urethane oligomer UA-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- Examples thereof include 306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoei Co., Ltd.).

The polymerizable compound preferably has an SP (Solubility Parameter) value of 9.50 or more, more preferably 10.40 or more, and even more preferably 10.60 or more.
Unless otherwise specified, the SP value in the present specification is determined by the Hoy method (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118). The unit of the SP value is omitted, but the unit is cal ^1/2 cm ^-3/2 .

The curable composition preferably contains a polymerizable compound containing a cardo skeleton from the viewpoint of improving the development residue.
As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

Equation (Q3)

In the above formula (Q3), Ar ^{11 to} Ar ¹⁴ each independently represent an aryl group containing a benzene ring surrounded by a broken line. X ^{1 to} X ⁴ each independently represent a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. a and b each independently represent an integer of 1 to 5, and c and d each independently represent an integer of 0 to 5. R ^{1 to} R ⁴ independently represent substituents, e, f, g and h each independently represent an integer of 0 or more, and the upper limits of e, f, g and h are Ar ^{11 to} Ar ^{14, respectively.} It is a value obtained by subtracting a, b, c or d from the number of substituents that can be contained. However, when Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each containing a benzene ring surrounded by a broken line as one of the fused rings, X ^{1 to} X ⁴ and R ^{1 to} R ⁴ are Each of them may be independently replaced with a benzene ring surrounded by a broken line, or may be replaced with a ring other than the benzene ring surrounded by a broken line.

In the formula (Q3), ^{the aryl group containing a benzene ring represented by Ar 11 to} Ar ¹⁴ is preferably an aryl group having 6 to 14 carbon atoms, and is preferably an aryl group having 6 to 10 carbon atoms (an aryl group having 6 to 10 carbon atoms). For example, it is more preferably a phenyl group (a phenyl group or a naphthyl group), and further preferably a phenyl group (only a benzene ring surrounded by a broken line).

In the formula (Q3), X ^{1 to} X ⁴ each independently represent a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. The ^{substituent containing the polymerizable group represented by X 1 to} X ⁴ is not particularly limited, but is preferably an aliphatic group containing a polymerizable group.
The ^{aliphatic group containing the polymerizable group represented by X 1 to} X ⁴ is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and has 2 to 10 carbon atoms. It is more preferable that it is an alkylene group of, and further preferably it is an alkylene group having 2 to 5 carbon atoms.
In ^{the aliphatic group containing a polymerizable group represented by X 1 to} X ⁴ , when the aliphatic group is substituted with a hetero atom, it is substituted with -NR- (R is a substituent), an oxygen atom and a sulfur atom. it is preferable that, -CH not adjacent in the aliphatic group 2 _- is more preferably is substituted with an oxygen atom or a sulfur atom, -CH nonadjacent in the aliphatic group 2 _- oxygen It is more preferably substituted with an atom. The ^{aliphatic group containing the polymerizable group represented by X 1 to} X ⁴ is preferably substituted at 1 to 2 sites by the hetero atom, more preferably at 1 site by the hetero atom, and Ar ¹¹ to 1. It is more preferable that one site adjacent to the aryl group containing the benzene ring surrounded by the broken line represented by Ar ^{14 is substituted with a heteroatom.}
The ^{polymerizable group contained in the aliphatic group containing the polymerizable group represented by X 1 to} X ⁴ is a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter, also referred to as a radical polymerizable group and a cationically polymerizable group, respectively). ) Is preferable.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and a suitable one can be a polymerizable group containing an ethylenically unsaturated bond capable of radical polymerization. Can be mentioned as a vinyl group, a (meth) acryloyloxy group and the like. Among them, the (meth) acryloyloxy group is preferable, and the acryloyloxy group is more preferable.
As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and vinyloxy. The groups can be mentioned. Of these, an alicyclic ether group and a vinyloxy group are preferable, and an epoxy group, an oxetanyl group and a vinyloxy group are particularly preferable.
The polymerizable group contained in the substituents contained in Ar ^{11 to} Ar ^{14 is preferably a radical polymerizable group.}
Two or more of the Ar ¹¹ to Ar ¹⁴ comprises a substituent containing a polymerizable ^group, preferably contains a substituent 2-4 of Ar 11 ^{to Ar 14} contains a polymerizable group, Ar ¹¹ is more preferably 2 or 3 of the to Ar ¹⁴ contains a substituent containing a polymerizable ^group, may contain a substituent group wherein two of Ar 11 ^{to Ar 14} contains a polymerizable group More preferred.
When Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each containing a benzene ring independently surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ are independently surrounded by a broken line. It may be replaced with a benzene ring or a ring other than the benzene ring surrounded by a broken line.

In the formula (Q3), a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably both a and b are 1.
In the formula (Q3), c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and more preferably both c and d are 0.

In formula (Q3), R ^{1 to} R ⁴ each independently represent a substituent. The ^{substituent represented by R 1 to} R ⁴ is not particularly limited, and for example, a halogen atom, an alkyl halide group, an alkyl group, an alkenyl group, an acyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, an aryl group and a hetero Examples thereof include an aryl group and an alicyclic group. The ^{substituent represented by R 1 to} R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group having 1 to 5 carbon atoms and an alkoxy group or a phenyl group having 1 to 5 carbon atoms. , Methyl group, methoxy group or phenyl group is more preferable.
In formula (Q3), when Ars ^{11 to Ar 14} are polycyclic aromatic hydrocarbon groups each containing a benzene ring surrounded by a broken line as one of the fused rings, R ^{1 to} R ⁴ are independent of each other. It may be replaced with a benzene ring surrounded by a broken line, or may be replaced with a ring other than the benzene ring surrounded by a broken line.

In the formula (Q3), e, f, g and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g and h are the substituents that ^{Ar 11 to} Ar ^{14 can contain, respectively.} It is a value obtained by subtracting a, b, c or d from the number.
e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and even more preferably 0.
When Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h may be 0 or 1. It is preferably 0, and more preferably 0.

Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. As the polymerizable compound containing a 9,9-bisarylfluorene skeleton, the compounds described in JP-A-2010-254732 can also be preferably used.

Examples of the polymerizable compound containing such a cardo skeleton include, but are not limited to, Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).

[Polyfunctional thiol compound]
The curable composition contains a polyfunctional thiol compound. As used herein, the polyfunctional thiol compound is intended to contain two or more thiol groups (that is, a group represented by -SH) in the same molecule.
The content of the polyfunctional thiol compound is not particularly limited, but is usually 1 to 10% by mass with respect to the content of the colorant. Among them, 1 to 5.5% by mass is preferable, and 1.5 to 3.5% by mass is more preferable, in that the curable composition has a more excellent effect of the present invention.
The content of the polyfunctional thiol compound is preferably 0.55 to 3.5% by mass, more preferably 0.8 to 2.0% by mass, based on the total solid content of the curable composition.
One type of polyfunctional thiol compound may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total is preferably within the above range.

The polyfunctional thiol compound is preferably a low molecular weight compound having a molecular weight of 100 or more, specifically, the molecular weight is preferably 100 to 1,500, and more preferably 150 to 1,000.
The polyfunctional thiol compound contains 2 or more thiol groups in the molecule, preferably 3 or more, preferably 10 or less, more preferably 6 or less, and 4 or less. It is more preferable to do so. Among them, the polyfunctional thiol compound is preferably trifunctional or higher, and more preferably trifunctional or tetrafunctional.
When the polyfunctional thiol compound is trifunctional or higher, the curable composition has a better effect of the present invention.

The polyfunctional thiol compound is preferably a compound having two or more groups represented by the following formula (1).

In formula (1), L ¹ represents a single bond or −CO−, and L ² represents a single bond or a divalent linking group.
As the polyfunctional thiol compound, a compound containing 2 to 6 groups represented by the formula (1) per molecule is preferable, a compound containing 2 to 4 is more preferable, and a compound containing 3 or 4 is further preferable. preferable.
^{As the divalent linking group in L 2} in the formula (1), a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) is divalent. aromatic group (e.g., arylene, substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein R ^{Reference numeral 31} is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), a combination thereof and the like.
When the divalent linking group is an alkylene group, the alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 2 carbon atoms.

As the polyfunctional thiol compound, a compound represented by the following formula (2) having two or more groups represented by the formula (1) is more preferable.

In formula (1), L ¹ represents a single bond or −CO−, and L ² represents a single bond or a divalent linking group. X represents an n-valent linking group, and n represents an integer of 2 to 6. The plurality of L ¹ and L ² may be the same or different from each other.

The aspects of L ¹ and L ² in the formula (2) are the same as those in the formula (1).
N in the formula (2) is preferably 2 to 4, more preferably 3 or 4.
As X, which is an n-valent linking group in the formula (2), a divalent linking group such as − (CH ₂ ) _m − (m represents an integer of 2 to 6); trimethylolpropane residue. , And − (CH ₂ ) _p − (p represents an integer of 2 to 6), a trivalent linking group such as an isocyanate ring; a tetravalent linking group such as a pentaerythritol residue; or 5 Valuable linking groups; hexavalent linking groups such as dipentaerythritol residues;

Specific examples of the polyfunctional thiol compound include 1,4-butanediol bis (thioglycolate), pentaerythritol tetra (3-mercaptopropionate), trimethylpropanthris (3-mercaptopropionate), and the like. Pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol Tetrakiss (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, and 1,4-bis (3-mercaptobutyloxy) butane, Examples thereof include 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.
Among them, the polyfunctional thiol compounds are pentaerythritol tetra (3-mercaptopropionate) and trimethylolpropanetris (3-mercaptopropio) in that the curable composition has a more excellent effect of the present invention. At least one selected from the group consisting of nate) is more preferred.

[Arbitrary component]
<Polymerization inhibitor>
The curable composition preferably contains a polymerization inhibitor. By containing a polymerization inhibitor, the curable composition has better stability over time. In the present specification, the term "stability over time" means that a cured film having an excellent pattern shape can be obtained even when the curable composition is prepared and stored for a predetermined period of time.
It is presumed that the polymerization inhibitor has an effect of suppressing the reaction between the polyfunctional thiol compound and the polymerizable compound in the curable composition during storage, and the above effect can be obtained.
The content of the polymerization inhibitor is preferably 0.1 to 1.5% by mass, more preferably 0.3 to 1.0% by mass, based on the content of the polyfunctional thiol compound.
When the content of the polymerization inhibitor is within the above range, the curable composition has better stability over time.
The content of the polymerization inhibitor is preferably 0.00055 to 0.055% by mass, more preferably 0.0015 to 0.01% by mass, based on the total solid content of the curable composition.

The polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used. Examples of the compound used as the polymerization inhibitor include phenol-based compounds, quinone-based compounds, hindered amine-based compounds, phenothiazine-based compounds, and nitrobenzene-based compounds. The above compounds may be used alone or in combination of two or more.

Examples of the phenolic compound include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-di-. tert-Butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, pentaerythritol tetrakis (3,5-di-tert) −Butyl-4-hydroxyhydrocinnamete), 4-methoxy-1-naphthol, 1,4-dihydroxynaphthalene and the like.

As the phenolic compound, the phenolic compound represented by the formula (IH-1) is preferable.

In the formula (IH-1), R _{1 to} R ₅ are independently hydrogen atom, alkyl group, alkenyl group, hydroxy group, amino group, aryl group, alkoxy group, carboxyl group, alkoxycarbonyl group, or acyl. Represents a group. R _{1 to} R ₅ may be connected to each other to form a ring.

_{Examples of R 1 to} R ₅ in the formula (IH-1) include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group and an ethyl group), and an alkoxy group having 1 to 5 carbon atoms (for example, methoxy). Groups and ethoxy groups, etc.), alkenyl groups having 2 to 4 carbon atoms (for example, vinyl groups, etc.), or phenyl groups are preferable.
Among them, R ₁ and R ₅ are independent of each other, a hydrogen atom or a tert-butyl group is more preferable, R ₂ and R ₄ are more preferably a _{hydrogen atom, R 3} is a hydrogen atom and an alkyl having 1 to 5 carbon atoms. A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.

Examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, 1,4-naphthoquinone and the like.

Examples of the hindered amine compound include a polymerization inhibitor represented by the following formula (IH-2).

_{R 6} in the formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Among them, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.
_{R 7 to} R ₁₀ in the formula (IH-2) independently represent a hydrogen atom or an alkyl group. As the _{alkyl group represented by R 7 to} R ₁₀ , an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

As the polymerization inhibitor, each of the above compounds may be used alone, in combination of two, or in combination of three or more.
The polymerization inhibitor preferably contains a phenolic compound. Among them, it is more preferable that the polymerization inhibitor contains two or more kinds of phenolic compounds. Curable compositions containing different phenolic compounds have better effects of the present invention.
The polymerization inhibitor preferably contains a phenolic compound and a hindered amine compound. A curable composition containing a phenolic compound and a hindered amine compound has a better effect of the present invention.

<Solvent>
The curable composition preferably contains a solvent. Examples of the solvent include water and an organic solvent. The curable composition preferably contains an organic solvent.
When the curable composition contains a solvent, the solid content of the curable composition is preferably 10 to 40% by mass. When the solid content of the curable composition is at least the lower limit, the viscosity is low and the coatability is improved. Further, since the concentration of the highly reactive compound is lowered, the stability over time is improved. When the solid content of the curable composition is not more than the upper limit, the viscosity is maintained to a certain degree and the coatability is improved. Further, the colorant having a heavy specific density is less likely to settle, and the stability over time is improved.

(Organic solvent)
When the curable composition contains an organic solvent, the content of the organic solvent is preferably 60 to 90% by mass with respect to the total mass of the curable composition.
The organic solvent may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the total amount thereof is preferably in the above range.

The organic solvent is not particularly limited, but for example, acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, 3-ethoxypropionic acid Examples thereof include methyl, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl 3-methoxypropionate, 2-heptanone, ethyl carbitol acetate, butyl carbitol acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and the like. ..

When two or more kinds of organic solvents are contained, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Preferably composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

(water)
The curable composition may contain water. Water may be intentionally added, or may be inevitably contained in the curable composition by adding each component contained in the curable composition.
The water content is preferably 0.01 to 1% by mass with respect to the total mass of the curable composition. When the water content is within the above range, the generation of pinholes is suppressed when the cured film is produced, and the moisture resistance of the cured film is further improved.

<Dispersant>
The curable composition preferably contains a dispersant. The dispersant contributes to improving the dispersibility of the colorant. In the present specification, the dispersant and the binder resin described later are different components.

When the curable composition contains a dispersant, the content of the dispersant is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the curable composition. 5, 5% by mass or more is more preferable, 11% by mass or more is particularly preferable, and 17% by mass or more is most preferable. The upper limit of the content of the dispersant is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 22% by mass or less, based on the total solid content of the curable composition.
When the content of the dispersant is 17% by mass or more, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
The dispersant may be used alone or in combination of two or more. When two or more kinds of dispersants are used in combination, the total amount is preferably within the above range.

As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Dispersants include polymer dispersants [for example, polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylics. Copolymers, naphthalene sulfonic acid formalin condensates], polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, pigment derivatives and the like can be mentioned.
Polymer compounds can be further classified into linear polymers, terminally modified polymers, graft-type polymers, and block-type polymers based on their structures.

(Polymer compound)
The polymer compound is adsorbed on the surface of the dispersant of the colorant (for example, an inorganic pigment) and acts to prevent the reaggregation of the disperse. Therefore, terminal-modified polymers, graft-type polymers, and block-type polymers containing an anchor site on the pigment surface are preferable.

The polymer compound preferably contains a structural unit containing a graft chain. In the present specification, "structural unit" is synonymous with "repeating unit".
Since the polymer compound containing a structural unit containing such a graft chain has an affinity with a solvent depending on the graft chain, the dispersibility of a colorant such as a black pigment and the dispersion stability after aging (aging Excellent stability). The polymer compound containing a structural unit containing a graft chain has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain. As a result, it becomes difficult to generate a residue in alkaline development.
The longer the graft chain, the higher the steric repulsion effect and the better the dispersibility of black pigments and the like. On the other hand, if the graft chain is too long, the adsorptive power to the coloring pigment such as the black pigment is lowered, and the dispersibility of the black pigment or the like tends to be lowered. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and excludes hydrogen atoms. It is more preferable that the number of atoms is 60 to 500.
Here, the graft chain indicates from the root of the main chain of the copolymer (atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure, and examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide. Examples include a structure and a polyether structure.
In order to improve the interoperability between the graft chain and the solvent, thereby increasing the dispersibility of the black pigment and the like, the graft chain was selected from the group consisting of polyester structure, polyether structure and poly (meth) acrylate structure. A graft chain containing at least one type is preferable, and a graft chain containing at least one of a polyester structure or a polyether structure is more preferable.

The macromonomer containing such a graft chain is not particularly limited, but a macromonomer containing a reactive double bond group can be preferably used.

Commercially available macromonomers that correspond to the structural unit containing the graft chain contained in the polymer compound and are suitably used for the synthesis of the polymer compound include AA-6 (trade name, manufactured by Toa Synthetic Co., Ltd.) and AA-10. (Product name, manufactured by Toa Synthetic Co., Ltd.), AB-6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AS-6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AN-6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AW -6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AA-714 (Product name, manufactured by Toa Synthetic Co., Ltd.), AY-707 (Product name, manufactured by Toa Synthetic Co., Ltd.), AY-714 (Product name, manufactured by Toa Synthetic Co., Ltd.) , AK-5 (trade name, manufactured by Toa Synthetic Co., Ltd.), AK-30 (trade name, manufactured by Toa Synthetic Co., Ltd.), AK-32 (trade name, manufactured by Toa Synthetic Co., Ltd.), Blemmer PP-100 (trade name, manufactured by Nikko). Blemmer PP-500 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PP-800 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer PP-1000 (trade name, manufactured by Nichiyu Co., Ltd.), Blemmer 55-PET -800 (Product name, manufactured by Nichiyu Co., Ltd.), Blemmer PME-4000 (Product name, manufactured by Nichiyu Co., Ltd.), Blemmer PSE-400 (Product name, manufactured by Nichiyu Co., Ltd.), Blemmer PSE-1300 (Product name, manufactured by Nichiyu Co., Ltd.) Blemmer 43PAPE-600B (trade name, manufactured by Nichiyu Co., Ltd.) and the like. Among these, AA-6 (trade name, manufactured by Toagosei), AA-10 (trade name, manufactured by Toagosei), AB-6 (trade name, manufactured by Toagosei), AS-6 (trade name, manufactured by Toagosei). Toagosei), AN-6 (trade name, manufactured by Toagosei), Blemmer PME-4000 (trade name, manufactured by Nichiyu) and the like are preferable.

The dispersant preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate, and cyclic or chain polyester. The dispersant more preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate, and chain polyester. It is more preferable that the dispersant contains at least one structure selected from the group consisting of a methyl polyacrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. The dispersant may contain the above-mentioned structures alone in one dispersant, or may contain a plurality of these structures in one dispersant.
Here, the polycaprolactone structure refers to a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opened structure of δ-valerolactone as a repeating unit.
Specific examples of the dispersant containing a polycaprolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 5. Specific examples of the dispersant containing the polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
Examples of dispersants containing polymethyl acrylate structure, X ⁵ in formula (4) is a hydrogen atom, and R ⁴ is a methyl group. Specific examples of dispersants containing polymethyl methacrylate structure, X ⁵ in formula (4) is a methyl group, and R ⁴ is a methyl group.

-Structural unit containing a graft chain The polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit containing a graft chain, and the following formula is preferable. It is more preferable to contain a structural unit represented by any one of (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4).

In formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ independently represent an oxygen atom or NH, respectively. W ¹ , W ² , W ³ and W ⁴ are preferably oxygen atoms.
In formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of synthetic constraints, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are preferably hydrogen atoms or alkyl groups having 1 to 12 carbon atoms (carbon atoms), respectively, from the viewpoint of synthetic constraints. Independently, a hydrogen atom or a methyl group is more preferred, and a methyl group is even more preferred.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly structurally restricted. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following linking groups (Y-1) to (Y-21). .. In the structures shown below, A and B mean binding sites, respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable because of the ease of synthesis.

In formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, but specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group and the like. Can be mentioned. Among these, ^{as the organic group represented by Z 1} , Z ² , Z ³ , and Z ⁴ , those containing a steric repulsion effect are preferable from the viewpoint of improving dispersibility, and each of them independently starts from 5 carbon atoms. Twenty-four alkyl groups or alkoxy groups are more preferable, and among them, branched alkyl groups having 5 to 24 carbon atoms, cyclic alkyl groups having 5 to 24 carbon atoms, or alkoxy groups having 5 to 24 carbon atoms are further preferable. .. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

In equations (1) to (4), n, m, p, and q are each independently an integer from 1 to 500.
In equations (1) and (2), j and k each independently represent an integer of 2-8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoint of stability over time and developability of the curable composition.

In the formula (3), R ³ represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. when p is 2 to 500, R ³ existing in plural numbers may be different from one another the same.
In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly structurally limited. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and 1 to 20 carbon atoms are preferable. The linear alkyl group of 1 to 6 is more preferable, and the linear alkyl group having 1 to 6 carbon atoms is further preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

The polymer compound can contain two or more structural units containing graft chains having different structures. That is, the molecule of the polymer compound may contain structural units represented by the formulas (1) to (4) having different structures from each other, and n, m, p in the formulas (1) to (4). When, and q each represent an integer of 2 or more, in the equations (1) and (2), j and k may contain structures different from each other in the side chain, and the equations (3) and (2) may be included. In 4), a plurality of R ³ , R ⁴ and X ⁵ existing in the molecule may be the same or different from each other.

The structural unit represented by the formula (1) is more preferably the structural unit represented by the following formula (1A) from the viewpoint of stability over time and developability of the curable composition.
The structural unit represented by the formula (2) is more preferably the structural unit represented by the following formula (2A) from the viewpoint of stability over time and developability of the curable composition.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same. Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoint of stability over time and developability of the curable composition. ..

Wherein (3A) or ^(3B), X ^3, Y 3, ^{Z 3} and p are as defined ^{X 3,} Y 3, ^{Z 3} and p in formula (3), and preferred ranges are also the same.

The polymer compound more preferably contains the structural unit represented by the formula (1A) as the structural unit containing the graft chain.

In the polymer compound, the structural unit containing the graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferable that it is contained in the range of 5 to 30%, and more preferably it is contained in the range of 5 to 30%. When the structural unit containing the graft chain is included in this range, the dispersibility of the black pigment is high and the developability at the time of forming the cured film is good.

-Hydrophobic structural unit The polymer compound preferably contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the graft chain). However, in the present specification, the hydrophobic structural unit is a structural unit having no acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

The hydrophobic structural unit is preferably a (corresponding) structural unit derived from a compound (monomer) having a ClogP value of 1.2 or more, and more preferably derived from a compound having a ClogP value of 1.2 to 8. It is a structural unit. Thereby, the effect of the present invention can be more reliably exhibited.

The ClogP value is determined by Daylight Chemical Information System, Inc. It is a value calculated by the program "CLOGP" that can be obtained from. This program provides the value of "calculated logP" calculated by Hansch, Leo's fragment approach (see literature below). The fragment approach is based on the chemical structure of a compound, and the logP value of the compound is estimated by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments. The details are described in the following documents. As used herein, the ClogP value is intended to be a value calculated by the program CLOGP v4.82.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.M. G. Sammenens, J. et al. B. Taylor and C.I. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev. , 93, 1281-1306, 1993.

logP means the common logarithm of the partition coefficient P (Partition Cofficient), and quantitatively describes how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is expressed by the following formula.
logP = log (Coil / Water)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Water represents the molar concentration of the compound in the aqueous phase.
When the logP value increases positively across 0, it means that oil solubility increases, and when it becomes negative and the absolute value increases, it means that water solubility increases, and there is a negative correlation with the water solubility of organic compounds, and the intimacy of organic compounds. It is widely used as a parameter for estimating water content.

The polymer compound preferably contains, as the hydrophobic structural unit, one or more structural units selected from the structural units derived from the monomers represented by the following formulas (i) to (iii).

In formulas (i) to (iii), R ¹ , R ² , and R ³ each independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 to 1. Represents an alkyl group of 6 (eg, methyl group, ethyl group, propyl group, etc.).
R ¹ , R ² , and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. It is more preferable that R ² and R ^{3 are hydrogen atoms.}
X represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

L is a single bond or divalent linking group. The divalent linking group includes a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) and a divalent aromatic group (for example, an arylene group). , substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} Examples include an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and a combination thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but a saturated aliphatic group is preferable. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, a heterocyclic group and the like.

The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group and the like.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle. The heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is fat. Group group, aromatic group or heterocyclic group), aliphatic group, aromatic group or heterocyclic group.

L is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more repeated oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is _{represented by − (OCH 2} CH ₂ ) n−, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z is an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group), Examples thereof include a heterocyclic group or a combination thereof. These groups an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} is an aliphatic group, an aromatic A group or heterocyclic group) or a carbonyl group (-CO-) may be contained.

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group further includes a ring-assembled hydrocarbon group and a crosslinked ring-type hydrocarbon group. Examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -Includes cyclohexylphenyl group and the like. As the crosslinked cyclic hydrocarbon ring, for example, pinan, bornan, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) and the like 2 Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane rings. , And tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodecane and 4-cyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene rings can be mentioned. Cross-linked cyclic hydrocarbon rings include fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydro. A fused ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenanthrene ring are condensed is also included.
As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, the aliphatic group does not have an acid group as a substituent.

The number of carbon atoms of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups and heterocyclic groups. However, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle. The heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups can be mentioned. However, the heterocyclic group does not have an acid group as a substituent.

In formula (iii), R ⁴ , R ⁵ , and R ⁶ are independently hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), and alkyl groups having 1 to 6 carbon atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.). For example, it represents a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Here, L and Z are synonymous with those in the above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

As the monomer represented by the formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, and L is a divalent linkage containing a single bond or an alkylene group or an oxyalkylene structure. A compound in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
As the monomer represented by the formula (ii), a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is used. preferable.
As the monomer represented by the formula (iii), a compound in which R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms or methyl groups and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable. ..

Examples of typical compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes and the like.
As examples of the representative compounds represented by the formulas (i) to (iii), the compounds described in paragraphs 089 to 093 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification. Is done.

In the polymer compound, the hydrophobic structural unit is preferably contained in the range of 10 to 90%, more preferably 20 to 80%, based on the total mass of the polymer compound in terms of mass. When the content is in the above range, good and sufficient pattern formation can be obtained.

-Functional groups capable of forming an interaction with a colorant such as a black pigment A polymer compound can introduce a functional group capable of forming an interaction with a colorant such as a black pigment. Here, it is preferable that the polymer compound further contains a structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment.
Examples of the functional group capable of forming an interaction with the colorant such as the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit containing an acid group, a structural unit containing a basic group, and a arrangement, respectively. It is preferable to contain a structural unit containing a coordinate group or a reactive structural unit.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be imparted with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, the curable composition contains the polymer compound as a dispersant that contributes to the dispersion of a colorant such as a black pigment. The curable composition containing such a polymer compound has excellent light-shielding properties in the exposed portion, and the alkali developability of the unexposed portion is improved.
When the polymer compound contains a structural unit containing an acid group, the polymer compound becomes more compatible with the solvent and the coatability tends to be improved.
This is because the acid group in the structural unit containing the acid group easily interacts with the colorant such as black pigment, the polymer compound stably disperses the colorant such as black pigment, and the colorant such as black pigment. It is presumed that this is because the viscosity of the polymer compound that disperses the polymer compound becomes low, and the polymer compound itself is easily dispersed stably.

The structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or a different structural unit, but may be the same as the hydrophobic structural unit described above. Is a different structural unit (ie, does not correspond to the above hydrophobic structural unit).

Examples of the acid group which is a functional group capable of forming an interaction with a colorant such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group and the like, and a carboxylic acid group and a sulfone. At least one of an acid group and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable in that it has good adsorption power to a colorant such as a black pigment and has high dispersibility of the colorant.
That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or more structural units containing an acid group.
The polymer compound may or may not contain a structural unit containing an acid group, but when it is contained, the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, it is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage to the image intensity due to alkaline development.

Examples of the basic group, which is a functional group capable of forming an interaction with a colorant such as a black pigment, include a heterocycle containing a primary amino group, a secondary amino group, a tertiary amino group, and an N atom. , And an amide group, and the preferred one is a tertiary amino group in that it has good adsorption power to a colorant such as a black pigment and has high dispersibility of the colorant. The polymer compound can contain one or more of these basic groups.
The polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total amount of the polymer compound in terms of mass. It is preferably 0.01% or more and 50% or less with respect to the mass, and more preferably 0.01% or more and 30% or less from the viewpoint of suppressing developmental inhibition.

Examples of the coordinating group which is a functional group capable of forming an interaction with a colorant such as a black pigment and the functional group having reactivity include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, and an acid anhydride. And acidified products and the like. Acetylacetoxy groups are preferred because they have good adsorption power to colorants such as black pigments and have high dispersibility of colorants. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it is contained, the content of these structural units. Is preferably 10% or more and 80% or less, more preferably 20% or more and 60% or less, based on the total mass of the polymer compound, from the viewpoint of suppressing developmental inhibition.

When the polymer compound contains, in addition to the graft chain, a functional group capable of forming an interaction with a colorant such as a black pigment, a functional group capable of forming an interaction with a colorant such as various black pigments described above may be used. It suffices if it is contained, and how these functional groups are introduced is not particularly limited, but the polymer compound is derived from the monomers represented by the following general formulas (iv) to (vi). It is preferable to contain one or more structural units selected from the structural units of.

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1. Represents an alkyl group of ~ 6 (eg, methyl group, ethyl group, propyl group, etc.).
In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are preferably independent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and more preferably independent of each other. Is a hydrogen atom or a methyl group. In the general formula (iv), ^{it is particularly preferable that R 12} and R ¹³ are hydrogen atoms, respectively.

_{X 1} in the formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.
Y in the formula (v) represents a methine group or a nitrogen atom.

_{L 1 in} formulas (iv) to (v) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), and divalent aromatic group (eg, substituted alkynylene group). , an arylene group, and a substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), substituted imino bond ^{(-NR 31} '- , wherein R ^{31 'is} an aliphatic group, an aromatic group or a heterocyclic group), carbonyl bond (-CO-), and, combinations thereof and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, aromatic groups and heterocyclic groups.

The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, aliphatic groups, aromatic groups and heterocyclic groups.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. One or more of other heterocycles, aliphatic rings or aromatic rings may be condensed on the heterocycle. The heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups can be mentioned.

L ₁ is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₁ may include a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is _{represented by − (OCH 2} CH ₂ ) n−, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with a colorant such as a black pigment other than the graft chain, and is a carboxylic acid group and a tertiary amino group. It is preferable, and it is more preferable that it is a carboxylic acid group.

In formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.) and alkyl groups having 1 to 6 carbon atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.) for example, a methyl group, an ethyl group, a propyl group, etc.), - _{Z 1,} or an _L 1 -Z _1. Wherein _{L 1} and _{Z 1} are the same meaning as _{L 1} and _{Z 1} in the above, it is the preferable examples. As R ¹⁴ , R ¹⁵ and R ¹⁶ , each independently has a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom is more preferable.

As the monomer represented by the formula (iv), R ¹¹ , R ¹² , and R ¹³ are independently hydrogen atoms or methyl groups, and L ₁ is a divalent group containing an alkylene group or an oxyalkylene structure. A compound having a linking group in which X ₁ is an oxygen atom or an imino group and Z ₁ is a carboxylic acid group is preferable.
As the monomer represented by the formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine group. Compounds are preferred.
Further, as the monomers represented by the formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms or methyl groups, L ₁ is a single bond or an alkylene group, and Z. _{A compound in which 1} is a carboxylic acid group is preferable.

Representative examples of the monomers (compounds) represented by the formulas (iv) to (vi) are shown below.
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction of a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) with succinic anhydride. A compound, a reaction product of a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and a phthalic acid anhydride, a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule, and a tetrahydroxyphthalic acid anhydride. Reactive product of, a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and a trimellitic anhydride, a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and a pyromellitic acid anhydride Examples thereof include a reaction product with, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenylmethacrylic acid and the like.

The content of the structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment is determined from the viewpoint of interaction with a colorant such as a black pigment, stability over time, and permeability to a developing solution. , 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, still more preferably 10% by mass to 70% by mass, based on the total mass of the polymer compound.

-Other structural units Further, the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a black color for the purpose of improving various performances such as image intensity, as long as the effects of the present invention are not impaired. A functional group having an affinity with another structural unit having various functions (for example, a dispersion medium used for a dispersion), which is different from a structural unit containing a functional group capable of forming an interaction with a colorant such as a pigment. Etc.) may be further provided.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
As the polymer compound, one or more of these other structural units can be used, and the content thereof is preferably 0% or more and 80% or less with respect to the total mass of the polymer compound in terms of mass. More preferably, it is 10% or more and 60% or less. Sufficient pattern formation is maintained when the content is in the above range.

-Physical Properties of Polymer Compounds The acid value of polymer compounds is preferably in the range of 0 mgKOH / g or more and 250 mgKOH / g or less, more preferably in the range of 10 mgKOH / g or more and 200 mgKOH / g or less, and 20 mgKOH / g or more and 120 mgKOH / g or less. The range is more preferred.
When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a cured film can be suppressed more effectively. When the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better. Further, when the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of a colorant such as a black pigment can be further suppressed, the number of coarse particles can be further reduced, and the stability of the curable composition over time can be improved. Can be improved further.

The acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. Further, a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group which is a constituent component of the polymer compound.

The weight average molecular weight of the polymer compound is 4, as a polystyrene conversion value by the GPC (Gel Permeation Chromatography) method, from the viewpoint of suppressing pattern peeling during development and developability when forming a cured film. It is preferably 000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. Is particularly preferable.
The GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID × 15 cm) as columns, and THF (tetrahydrofuran) as an eluent. ..

The polymer compound can be synthesized based on a known method, and examples of the solvent used in synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, Examples thereof include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound include "DA-7301" manufactured by Kusunoki Kasei Co., Ltd., "Disperbyk-101 (polyamidoamine phosphate)" manufactured by BYK Chemie Co., Ltd., 107 (carboxylic acid ester), 110 (copolymer containing an acid group). ), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) "," BYK-P104, P105 (non-high molecular weight) "Saturated polycarboxylic acid", EFKA 4047, 4050-4010-4165 (polyurethane type), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 ( High molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”, Ajinomoto Fine Techno Co., Ltd.“ Azispar PB821, PB822, PB880, PB881 ”, Kyoeisha Chemical Co., Ltd.“ Floren TG-710 (urethane oligomer) ”,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”, Kusumoto Kasei Co., Ltd.“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid) ), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", Kao" Demor RN, N (naphthalene sulfonate formalin copolymer), MS, C, SN-B (Aromatic formalin sulfonate polycondensate) ”,“ Homogenol L-18 (polymer polycarboxylic acid) ”,“ Emargen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ Acetamine 86 (stearyl) "Aminacetate)", Nippon Lubrizol "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer containing a functional part at the end) ), 24000, 28000, 32000, 38500 (graft copolymer) ", Nikko Chemicals" Nikkor T106 (polyoxyethylene sorbitan monooleart), MYS-IEX (polyoxyethylene monostearate) ", Kawaken Fine Chemicals Hinoact T-8000E, etc., Shinetsu Chemical Industry Co., Ltd., Organosiloxane Polymer KP341, Yusho "W001: Cationic Surfactant", Polyoxyethylene Lauryl Ether, Polyoxyethylene Stearyl Ether, Polyoxyethylene Oleyl Ether, Polyoxyethylene Octylphenyl Ether, Polyoxyethylene Nonylphenyl Ether, Polyethylene Glycol Dilaurate, Polyethylene Glycol Distea Nonionic surfactants such as rate and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", Morishita Sangyo "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer" 400, EFKA Polymer 401, EFKA Polymer 450 ”, polymer dispersants such as Sannopco“ Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 ”, ADEKA“ Adecapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ", Sanyo Kasei" Ionet (trade name) S-20 ", etc. Can be mentioned. Further, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can also be used.
Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2001, DISPERBY, manufactured by Big Chemie. Examples thereof include DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajinomoto Fine-Techno's Ajispar PB821, Ajispar PB822, and Ajispar PB881.
These polymer compounds may be used alone or in combination of two or more.

As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.

As the dispersant, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 (corresponding paragraphs 0075 to 0133 of US2011 / 0124824) of JP2010-106268A can be used, and the contents thereof. Can be incorporated and incorporated herein by reference.
In addition to the above, a configuration containing a side chain structure in which acidic groups of paragraphs 0028 to 0084 of JP2011-153283 (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) are bonded via a linking group. High molecular weight compounds containing the components can be used, the contents of which can be incorporated and incorporated herein by reference.

<Binder resin>
The curable composition preferably contains a binder resin.
The content of the binder resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.9% by mass or more, based on the total solid content of the curable composition. 9% by mass or more is particularly preferable, 30% by mass or less is preferable, 25% by mass or less is more preferable, 18% by mass or less is further preferable, and 10% by mass or less is particularly preferable.
When the content of the binder resin is 1.9% by mass or more and 10% by mass or less, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
As the binder resin, one type may be used alone, or two or more types may be used in combination. When two or more kinds of binder resins are used in combination, the total amount thereof is preferably within the above range.

As the binder resin, it is preferable to use a linear organic polymer. As such a linear organic polymer, known ones can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weakly alkaline water is selected to allow water or weakly alkaline water development. Among them, as the binder resin, an alkali-soluble resin (a resin containing a group that promotes alkali solubility) is particularly preferable.
The binder resin is a linear organic polymer that promotes at least one alkali solubility in the molecule (preferably a molecule having a (meth) acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from the alkali-soluble resins containing the group to be used. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, (meth) acrylic / (meth) acrylamide copolymer resin, epoxy resin and A polyimide resin is preferable, and a (meth) acrylic resin, a (meth) acrylamide resin, a (meth) acrylic / (meth) acrylamide copolymer resin or a polyimide resin is more preferable from the viewpoint of controllability of developability.
Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Among them, those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution are preferable, and alkali-soluble resins containing a structural unit derived from (meth) acrylic acid are more preferable. These acid groups may be only one kind or two or more kinds.

Examples of the binder resin include radical polymers containing a carboxylic acid group in the side chain. Examples of the radical polymer containing a carboxylic acid group in the side chain include Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Application Laid-Open No. 54-34327, Japanese Patent Application Laid-Open No. 58-125777, Japanese Patent Application Laid-Open No. 54-25957, and Japanese Patent Application Laid-Open No. 54-54. Examples thereof include those described in JP-A-92723, JP-A-59-53836, and JP-A-59-71048. Examples of the radical polymer containing a carboxylic acid group in the side chain include a resin obtained by singly or copolymerizing a monomer containing a carboxylic acid group, and an acid anhydride obtained by singly or copolymerizing a monomer containing an acid anhydride. Examples thereof include a resin obtained by hydrolyzing, half-esterifying or half-amidizing the unit, and an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride.
Examples of the monomer containing a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene and the like. An acidic cellulose derivative containing a carboxylic acid group in the side chain is also mentioned as an example.
Examples of the monomer containing an acid anhydride include maleic anhydride and the like. In addition to this, a polymer containing a hydroxyl group to which a cyclic acid anhydride is added is useful.
Acetal-modified polyvinyl alcohol-based binder resins containing an acid group are described in European Patent No. 9993966, European Patent No. 1204000, JP-A-2001-318436, and the like. The acetal-modified polyvinyl alcohol-based binder resin containing an acid group is suitable because it has an excellent balance between film strength and developability.
Further, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. Further, in order to increase the strength of the cured film, alcohol-soluble nylon and polyether, which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, are also useful.
The polyimide resin described in International Publication No. 2008/123097 is also useful.

Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer if necessary] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / as required Other addition-polymerizable vinyl monomers] The copolymer is suitable because it has an excellent balance of film strength, sensitivity, and developability.
Examples of commercially available products include Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai), and Cyclomer P (ACA) 230AA manufactured by Daicel Ornex.

For the production of the binder resin, for example, a known method by a radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent when producing a binder resin by the radical polymerization method can be easily set by those skilled in the art.

As the binder resin, it is also preferable to use a polymer containing a structural unit containing a graft chain and a structural unit containing an acid group (alkali-soluble group).
The definition of the structural unit containing the graft chain is synonymous with the structural unit containing the graft chain contained in the above-mentioned dispersant, and the preferable range is also the same.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group and the like, and at least one of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group is preferable. Carboxylic acid groups are more preferred.

(Structural unit containing acid group)
As the structural unit containing an acid group, it is preferable to contain one or more structural units selected from the structural units derived from the monomers represented by the following formulas (vii) to (ix).

In formulas (vii) to formula (ix), R ²¹ , R ²² , and R ²³ each independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1. Represents an alkyl group of ~ 6 (eg, methyl group, ethyl group, propyl group, etc.).
In formulas (vii) to formula (ix), R ²¹ , R ²² , and R ²³ are preferably hydrogen atoms independently or alkyl groups having 1 to 3 carbon atoms, respectively, and each of them is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It is more preferably a methyl group. In the formula (vii), ^{it is particularly preferable that R 21} and R ²³ are hydrogen atoms, respectively.

_{X 2} in the formula (vii) represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.
Y in the formula (viii) represents a methine group or a nitrogen atom.

_{L 2} in the formulas (vii) to (ix) represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), and divalent aromatic group (eg, substituted alkynylene group). , an arylene group, and a substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), substituted imino bond ^{(-NR 41} '- , Here, R ^41'is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), and a combination thereof.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, aromatic groups and heterocyclic groups.

The number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, aliphatic groups, aromatic groups and heterocyclic groups.

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. One or more of other heterocycles, aliphatic rings or aromatic rings may be condensed on the heterocycle. The heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxy group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ⁴² , where R ⁴² is fat. Group groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups can be mentioned.

L ₂ is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₂ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is _{represented by − (OCH 2} CH ₂ ) n−, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In formulas (vii) to (ix), Z ₂ is an acid group, preferably a carboxylic acid group.

In formula (ix), R ²⁴ , R ²⁵ , and R ²⁶ are independently hydrogen atoms, halogen atoms (eg, fluorine, chlorine, bromine, etc.), and alkyl groups having 1 to 6 carbon atoms (eg, methyl). group, an ethyl group, a propyl group, etc.), - represents a _{Z 2,} or _L 2 -Z _2. Here _{L 2} and _{Z 2} has the same meaning as _{L 2} and _{Z 2} in the above, and preferred examples are also the same. As R ²⁴ , R ²⁵ , and R ²⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

As the monomer represented by the formula (vii), R ²¹ , R ²² , and R ²³ are independently hydrogen atoms or methyl groups, and L ₂ is a divalent group containing an alkylene group or an oxyalkylene structure. _{A compound in which X 2} is an oxygen atom or an imino group and Z ₂ is a carboxylic acid group is preferable as a linking group.
As the monomer represented by the formula (vii), R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is a methine group. Compounds are preferred.
Further, as the monomer represented by the formula (ix), a compound in which R ²⁴ , R ²⁵ , and R ²⁶ are independently hydrogen atoms or methyl groups and Z ₂ is a carboxylic acid group is preferable.

The binder resin can be synthesized by the same method as the dispersant containing the structural unit containing the graft chain described above, and its preferable acid value and weight average molecular weight are also the same.

The binder resin may have one or more structural units containing an acid group.
The content of the structural unit containing an acid group is preferably 5 to 95% of the total mass of the binder resin in terms of mass, and is 10 to 90 from the viewpoint of suppressing damage to the image intensity due to alkaline development. More preferably.

<Surfactant>
The curable composition preferably contains a surfactant. The surfactant contributes to improving the coatability of the curable composition.

When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, preferably 0.005 to 2.0% by mass, based on the total mass of the curable composition. More preferably 1.0% by mass.
As the surfactant, one type may be used alone, or two or more types may be used in combination. When two or more kinds of surfactants are used in combination, the total amount is preferably within the above range.

Examples of the surfactant include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant.

For example, when the curable composition contains a fluorine-based surfactant, the liquid properties (particularly, fluidity) of the curable composition are further improved. That is, when a film is formed using a curable composition containing a fluorine-based surfactant, the wettability to the surface to be coated is improved by reducing the interfacial tension between the surface to be coated and the coating liquid. , The applicability to the surface to be coated is improved. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and / or liquid saving, and has good solubility in a curable composition. ..

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, F780 (above, DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, Examples thereof include PF6320, PF6520, and PF7002 (manufactured by OMNOVA).
A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include the compounds described in JP-A-2011-89090. The compound (F-1) represented by the following formula is also mentioned as a fluorine-based surfactant. In compound (F-1), the structural units represented by the formulas (A) and (B) are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a, b, and c satisfy the relations of a + c = 14 and b = 17, respectively. The weight average molecular weight of the following compounds is, for example, 15,311.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, and polyoxyethylene. Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (BASF's Pluronic L10, L31, L61, L62, Examples thereof include 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) and Solsparse 20000 (Nippon Lubrizol Co., Ltd.). Further, Pionin D-6112-W manufactured by Takemoto Oil & Fat Co., Ltd. and NCW-101, NCW-1001 and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specifically, as cationic surfactants, phthalocyanine derivatives (trade name, EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shinetsu Chemical Industry Co., Ltd.), (meth) acrylic acid-based (meth) acrylic acid-based (meth) Co) Polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yusho Co., Ltd.) and the like can be mentioned.

Specific examples of the anionic surfactant include W004, W005, W017 (Yusho Co., Ltd.) and the like.

Examples of the silicone-based surfactant include "Torre Silicone DC3PA", "Torre Silicone SH7PA", "Torre Silicone DC11PA", "Torre Silicone SH21PA", "Torre Silicone SH28PA" and "Torre Silicone SH28PA" manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA ”,“ Torre Silicone SH30PA ”,“ Torre Silicone SH8400 ”,“ TSF-4440 ”,“ TSF-4300 ”,“ TSF-4445 ”,“ TSF-4460 ”,“ TSF -4452 ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shinetsu Silicone Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by Big Chemie, and the like.

<Silane coupling agent>
The silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. A hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by a hydrolyzing reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the number of carbon atoms thereof is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
When forming a cured film on a substrate, the silane coupling agent contains fluorine atoms and silicon atoms (excluding silicon atoms to which a hydrolyzable group is bonded) in order to improve the adhesion between the substrate and the cured film. It is preferable that there is no fluorine atom, silicon atom (excluding silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and 3 carbon atoms. It is desirable that the above-mentioned split-chain alkyl groups are not included.

The silane coupling agent preferably contains a group represented by the following formula (Z). * Represents the bond position.
Formula (Z) * -Si- (R _Z1 ) ₃
In formula (Z), R _Z1 represents a hydrolyzable group, the definition of which is as described above.

The silane coupling agent preferably contains one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group. The curable functional group may be directly bonded to the silicon atom or may be bonded to the silicon atom via the linking group.
A radically polymerizable group is also mentioned as a preferable embodiment of the curable functional group contained in the silane coupling agent.

The molecular weight of the silane coupling agent is not particularly limited, and from the viewpoint of handleability, it is often 100 to 1,000, preferably 270 or more, and more preferably 270 to 1,000.

One of the preferred embodiments of the silane coupling agent is the silane coupling agent X represented by the formula (W).
Equation (W) R _Z2- Lz-Si- (R _Z1 ) ₃
R _z1 represents a hydrolyzable group, as defined above.
R _z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. If Lz represents a divalent linking group, the divalent As the linking group, an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 ^{-, -} CONR _{^{12 -, - CO -, -}} CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof. Among them, at least one selected from the group consisting of an alkylene group optionally substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group optionally substituted with a halogen atom having 6 to 12 carbon atoms, or at least one selected from the group. these groups and ^{-NR 12 -, - CONR 12 -} , - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S-, and SO ₂ -, at least selected from the group consisting of group is preferred, which consist of a combination of one group, an alkylene group optionally substituted with a halogen atom having 2 to 10 carbon _{atoms, -CO 2 -, - O -} , - CO -, - CONR 12 -, or , A group consisting of a combination of these groups is more preferable. Here, R ¹² represents a hydrogen atom or a methyl group.

Examples of the silane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name KBM-602) and N-β-aminoethyl-γ-aminopropyl-tri. Methoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name KBE-602), γ-aminopropyl- Trimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name KBM-903), γ-aminopropyl-triethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name KBE-903), 3-methacryloxypropyltrimethoxysilane (Shinetsu Chemical Co., Ltd.) Examples thereof include glycidoxyoctyltrimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name KBM-4803) and the like, which are manufactured by Kogyo Co., Ltd. and have a trade name of KBM-503).

Another preferred embodiment of the silane coupling agent is a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule, and containing a hydrolyzable group bonded to the silicon atom. Can be mentioned.
The silane coupling agent Y may have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different. The atoms and substituents that can be bonded are hydrogen atom, halogen atom, hydroxyl group, alkyl group having 1 to 20 carbon atoms, alkenyl group, alkynyl group, aryl group, alkyl group and / or amino group substitutable with aryl group, silyl. Examples thereof include a group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group. These substituents further include an amino group, a halogen atom, a sulfonamide group, which can be substituted with a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group. It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxylic acid group, or a salt thereof, a sulfo group, a salt thereof or the like.
At least one hydrolyzable group is bonded to the silicon atom. The definition of hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by the formula (Z).

The silane coupling agent Y preferably has at least one nitrogen atom in the molecule, and the nitrogen atom preferably exists in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably contains at least one organic group. The structure of the amino group may be present in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may be present as a substituted amino group such as aniline.
Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent, and the substituents that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom and a sulfonamide. Examples thereof include a group, an alkoxycarbonyl group, a carbonyloxy group, an amide group, a urea group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxylic acid group, or a salt thereof, a sulfo group and the like.
The nitrogen atom is preferably bonded to a curable functional group via any organic linking group. Preferred organic linking groups include the above-mentioned nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferable range is also as described above.
The silane coupling agent Y may have at least one curable functional group in one molecule, but may also contain two or more curable functional groups. From the viewpoint of sensitivity and stability, it is preferable to contain 2 to 20 curable functional groups in the molecule, more preferably 4 to 15 and even more preferably 6 to 10.

The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but the above range (preferably 270 or more) can be mentioned.

The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content in the curable composition. .0 to 6% by mass is more preferable.

The curable composition may contain one type of silane coupling agent alone, or may contain two or more types. When the curable composition contains two or more kinds of silane coupling agents, the total may be within the above range.

<UV absorber>
The curable composition may contain an ultraviolet absorber. As a result, the shape of the pattern of the cured film can be made more excellent (fine).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples thereof, compounds of paragraphs 0137 to 0142 of JP2012-068418 (corresponding paragraphs 027 to 0254 of US2012 / 0068292) can be used, and these contents can be incorporated and incorporated in the present specification. ..
In addition, a diethylamino-phenylsulfonyl UV absorber (manufactured by Daito Chemical Co., Ltd., trade name, UV-503) and the like are also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, further preferably 0.1 to 5% by mass, based on the total solid content of the curable composition. preferable.

[Method for producing curable composition]
The method for producing a curable composition includes the following mixing and dispersing steps. It preferably includes a standing step and / or a filtering step. Hereinafter, preferred embodiments of each step will be described in detail.

[Mixing and dispersion steps]
The mixing and dispersing steps are steps of mixing the above components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser) to obtain a curable composition. In the mixing and dispersing steps, each component constituting the curable composition may be collectively blended, or each component may be dissolved or dispersed in an organic solvent and then sequentially blended. The order of charging and working conditions at the time of blending are not particularly limited. The mixing and dispersing steps may include a step of preparing a dispersion liquid.

(Step to prepare dispersion)
The step of preparing the dispersion liquid is a step of mixing the colorant, the dispersant, and the solvent, and dispersing the colorant by the above method to prepare the dispersion liquid. Other components can be mixed with the prepared dispersion to produce a curable composition.
Examples of the mechanical force used to disperse the pigment in the step of producing the dispersion liquid include compression, squeezing, impact, shearing and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization and ultrasonic dispersion. In addition, "Dispersion Technology Taizen, published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and practical comprehensive data collection of industrial applications, published by Management Development Center" The processes and dispersers described in "Published by the Department, October 10, 1978" can be preferably used.
In the step of producing the dispersion liquid, the pigment may be miniaturized by the salt milling step. As the materials, equipment, processing conditions, etc. used in the salt milling step, those described in JP-A-2015-194521 and JP-A-2012-046629 can be used, for example.
The method for producing the curable composition preferably includes a step of obtaining the colorant by a thermal plasma method. The step of obtaining the colorant is carried out before mixing each of the above components. The specific mode of the manufacturing process of the colorant by the thermal plasma method is as described above.

<Standing process>
The colorant may undergo the following standing steps before being subjected to a mixing and dispersing step or a step of preparing a dispersion liquid.
The standing step is a predetermined time (preferably 12 to 72 hours, more preferably 12 to 72 hours) in a closed container in which the colorant obtained by the thermal plasma method is not exposed to the atmosphere after its production and the oxygen concentration is controlled. It is a step of allowing to stand for 12 to 48 hours, more preferably 12 to 24 hours). At this time, it is more preferable that the water content in the closed container is controlled.

At this time, the oxygen (O ₂ ) concentration and the water content in the closed container are each preferably 100 ppm or less, more preferably 10 ppm or less, and further preferably 1 ppm or less.
The oxygen (O ₂ ) concentration and the water content in the closed container can be adjusted by adjusting the oxygen concentration and the water content in the inert gas supplied into the closed container. As the inert gas, nitrogen gas and argon gas are preferably used, and among these, nitrogen gas is more preferably used.
After the above-mentioned standing step, the surface of the colorant and the grain boundaries become stable. Thereby, the generation of pinholes in the cured film obtained by curing the curable composition can be suppressed.
The standing step can be replaced by the step H described in the method for producing a colorant, and the curable composition is preferably replaced by the step H in that the curable composition has a more excellent effect of the present invention. ..

<Filtration process>
The filtration step is a step of filtering the curable composition produced by the above mixing and dispersing steps with a filter. In the filtration step, foreign matter can be removed from the curable composition and / or defects can be reduced.
The filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like. Examples thereof include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (containing high density and ultra-high molecular weight). .. Among these materials, polypropylene (containing high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and about 0.3 to 0.7 μm. More preferred. Within this range, it is possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the pigment while suppressing the filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the pore diameters of the second and subsequent times are the same or larger than the pore diameter of the first filtering. First filters having different pore diameters within the above range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., and the like. ..
As the second filter, one formed of the same material as the first filter described above can be used. The pore size of the second filter is preferably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

[Curing film (light-shielding film)]
The cured film is obtained by curing the curable composition. The cured film contains a colorant. The cured film is preferably used as a light-shielding film, and specifically, is preferably used for light-shielding the peripheral portion of the light receiving portion of the image sensor.
Hereinafter, a case where the cured film is used as a light-shielding film in the peripheral portion of the light receiving portion of the image sensor will be described as an example.

The film thickness of the light-shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and 0.3 μm or more and 10 μm or less, in that the light-shielding film has a more excellent effect of the present invention. Is more preferable, and 0.3 μm or more and 5 μm or less is further preferable. Since the curable composition has a high optical density per unit volume (because it has a high light-shielding property), it is possible to reduce the film thickness as compared with the conventional curable composition using a black pigment.
The size of the light-shielding film (the length of one side of the light-shielding film provided around the light receiving portion of the sensor) is preferably 0.001 mm or more and 10 mm or less because the light-shielding film has a more excellent effect of the present invention. It is more preferably 05 mm or more and 7 mm or less, and further preferably 0.1 mm or more and 3.5 mm or less.

[Manufacturing method of cured film]
Next, a method for producing a cured film (light-shielding film) will be described.
Hereinafter, the manufacturing method will be described in detail for each step.

The method for producing a cured film includes the following curable composition layer forming step and exposure step. The method for producing the cured film preferably further includes a developing step.
Curable composition layer forming step: A step of forming a curable composition layer on a support.
Exposure step: A step of exposing the curable composition layer.
Development step: A step of developing a curable composition layer after exposure to form a patterned cured film (light-shielding film).

Specifically, the curable composition is applied directly or via another layer onto the substrate to form a curable composition layer (curable composition layer forming step), and a predetermined mask pattern is formed. The cured film can be produced by exposing only the coated film portion irradiated with light (exposure step) and developing with a developing solution (development step).
Hereinafter, each of the above steps will be described.

<Curable composition layer forming step>
The curable composition layer forming step is a step of forming a curable composition layer on a support (hereinafter, also referred to as “substrate”). Among them, it is preferable to include a coating step of applying the curable composition on the support to form a curable composition layer, and the curable composition is directly applied on the support to form the curable composition layer on the support. It is more preferable to include a coating step of forming a curable composition layer.
Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, and those to which a transparent conductive film is attached, photoelectric used for solid-state image sensors, and the like. Examples thereof include a conversion element substrate (for example, a silicon substrate), a CCD (Charge Coupled Device) substrate, a CMOS (Complementary Metal-Oxide Semiconductor) substrate, and the like.
If necessary, an undercoat layer may be provided on these substrates to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface of the substrate.

As a method for applying the curable composition on the substrate, various coating methods such as slit coating, inkjet method, rotary coating, cast coating, roll coating, and screen printing method can be applied.

When producing a color filter containing a black matrix for a solid-state image sensor, the coating film thickness of the curable composition is preferably 0.35 μm or more and 1.5 μm or less from the viewpoint of resolution. More preferably, it is 40 μm or more and 1.0 μm or less.

The curable composition applied on the substrate is usually dried at 70 ° C. or higher and 110 ° C. or lower under the conditions of 2 minutes or more and 4 minutes or less. This makes it possible to form a curable composition layer.

<Exposure process>
The exposure step is a step of exposing the curable composition layer (coating film) formed in the curable composition layer forming step through a mask and curing only the light-irradiated coating film portion.
The exposure is preferably carried out by irradiation with active light rays or radiation, and in particular, ultraviolet rays such as g-rays, h-rays, and i-rays are preferable, and a high-pressure mercury lamp is more preferable. Exposure is not particularly limited but is preferably 200 mJ / cm ² or more, more preferably 200~1,500mJ / cm ^2, more preferably ^{200~1,000mJ / cm 2, 200~500mJ / cm} 2 is particularly preferred. When the exposure amount is within the above range, the method for producing a cured film has better stability and productivity.
From the viewpoint of improving resolution, exposure with an i-line stepper is preferable in forming a light-shielding film for a solid-state image sensor.

<Development process>
The developing step is a step of developing the exposed curable composition layer. A patterned cured film can be obtained by the developing process.
The method for producing the cured film preferably includes a developing step and the following cleaning step. In the developing step, an alkaline developing process (development step) is performed to elute the unirradiated portion of the light in the exposure step into an alkaline aqueous solution. As a result, only the photocured portion (light-irradiated coating film portion) remains.
As the developing solution, when producing a light-shielding color filter containing a black matrix for a solid-state image sensor, an organic alkaline developing solution that does not cause damage to the underlying circuit or the like is preferable. The developing temperature is usually preferably 20 to 30 ° C., and the developing time is preferably 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. As the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, or sodium metasilicate has a concentration of 0.001 to 10% by mass, preferably 0.01 to 1. An alkaline aqueous solution dissolved so as to be by mass% can be mentioned. Organic developing solutions include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5.4.0]-. Examples thereof include an alkaline aqueous solution in which an alkaline compound such as 7-undecene is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant can be added to the alkaline aqueous solution. As the developing method, for example, a paddle developing method and a shower developing method can be used.

<Washing process>
The cleaning step is a step of cleaning (rinsing) the developed curable composition layer with pure water or the like. The cleaning method is not particularly limited, and a known cleaning method can be used.

The method for producing the cured film may include, after the developing step, a post-baking step of heating the cured film and / or a curing step of exposing the cured film to the entire surface.

A color filter containing a cured film (black matrix) is suitable for a solid-state image sensor such as a CCD image sensor and / or a CMOS image sensor. In particular, it is suitable for a high resolution CCD image sensor and / or a CMOS image sensor having more than 1 million pixels. That is, the color filter containing the cured film is suitable for a solid-state image sensor. The color filter may include a structure in which a cured film forming each color pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
The cured film (black matrix) is arranged between, for example, a light receiving portion of each pixel constituting a CCD image sensor and / or a CMOS image sensor, and a microlens for condensing light.

[Solid image sensor]
The solid-state image sensor contains the cured film (black matrix). The solid-state image sensor preferably contains a color filter that contains a black matrix and, if necessary, a patterned film composed of pixels of other colors (3 or 4 colors).
The solid-state image sensor is not particularly limited as long as it contains the black matrix and functions as a solid-state image sensor. For example, a light-receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) is formed on a substrate. Examples thereof include a solid-state image sensor containing a light receiving element made of a plurality of photodiodes, polysilicon and the like, and containing the black matrix on the surface opposite to the light receiving element forming surface of the substrate.
The color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the solid-state image pickup device containing such a structure include the solid-state image pickup devices described in JP-A-2012-227478 and JP-A-2014-179757.

[Image display device]
The cured film can be suitably used for an image display device (for example, a liquid crystal display device, an organic electroluminescence display device, etc.).

For details on the definition of image display devices and the details of each image display device, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)" and "Display Device (by Junaki Ibuki, Industrial Books)". (Issued in 1989) ”etc. The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The cured film is suitable, for example, for a liquid crystal display device of the type described in the above-mentioned "next-generation liquid crystal display technology".

One aspect of the liquid crystal display device containing the cured film is, for example, a color filter, a liquid crystal layer, and a liquid crystal driving means (simple matrix driving method, and an active matrix driving method) between a pair of substrates whose at least one is light-transmitting. A liquid crystal display device containing at least a method) can be mentioned. The liquid crystal display device contains a plurality of pixel groups, and each pixel constituting the pixel group contains a color filter in which images are separated from each other by the cured film (black matrix).

In another aspect of the liquid crystal display device, at least one is contained between a pair of light-transmitting substrates, a color filter, a liquid crystal layer, and a liquid crystal driving means, and the liquid crystal driving means is an active element (for example, a TFT (for example, TFT). A color filter containing a Thin Film Transistor)) and containing the cured film (black matrix) between the active elements.

The color filter containing the cured film is suitable for a color TFT (Thin Film Transistor) type liquid crystal display device. A color TFT liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Publishing Co., Ltd. in 1996)". Further, the color filter is a liquid crystal display device having an enlarged viewing angle such as a transverse electric field drive method such as IPS (In Plane Switching); a pixel division method such as MVA (Multi-domine Vertical Element); STN (Super-Twist). Suitable for Nematic), TN (Twisted Nematic), VA (Vertical Element), OCS (on-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical).

The color filter is suitable for a bright and high-definition COA (Color-filter On Array) type liquid crystal display device. In the COA type liquid crystal display device, the required characteristics for the color filter may be required for the interlayer insulating film, that is, low dielectric constant and resistance to the stripping liquid, in addition to the usual required characteristics. The COA type liquid crystal display device containing the above color filter has better resolution or better durability. In addition, in order to satisfy the required characteristics of low dielectric constant, a resin film may be further contained on the color filter layer.

These image display methods are described, for example, on page 43 of "EL, PDP, LCD Display-Latest Trends in Technology and Market- (Toray Research Center Research Division, 2001)". In the above, EL stands for Electroluminescence, PDP stands for Plasma Display Panel, and LCD stands for liquid crystal display.

In addition to the color filter, the liquid crystal display device is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter can be applied to a liquid crystal display device composed of these known members. Regarding these materials, for example, "'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima Co., Ltd., published in 1994)" and "2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2) (Omote Yoshikichi) Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding the backlight, SID meeting Digest 1380 (2005) (A. Konno et. Al) and / or Monthly Display December 2005 issue, pages 18 to 24 (Yasuhiro Shima), pages 25 to 30 (Takaaki Yagi). It is described in.

The cured film is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone and a digital camera; an OA (Office Automation) device such as a printer compound machine and a scanner; a surveillance camera, a bar code reader, and an automatic cash deposit / payment machine ( ATM: automated teller machine), industrial equipment such as personal authentication using high-speed cameras and face image authentication; in-vehicle camera equipment; medical camera equipment such as endoscopes, capsule endoscopes and catheters; biosensors, Optical filters used in biosensors, military reconnaissance cameras, stereoscopic map cameras, meteorological and oceanographic observation cameras, land resource exploration cameras, and space equipment such as exploration cameras for space astronomical and deep space targets. It is suitable for a light-shielding member and a light-shielding layer of a module, and further as an antireflection member and an antireflection layer.

The cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The cured film is suitable for optical filters and optical films used for micro LEDs and micro OLEDs, as well as members for imparting a light-shielding function or an antireflection function.
Examples of the micro LED and the micro OLED include those described in the special table 2015-500562 and the special table 2014-533890.

The cured film is suitable as an optical and optical film used in a quantum dot display. Further, the cured film is suitable as a member for imparting a light-shielding function and an antireflection function.
Examples of quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960. The ones described are mentioned.

Hereinafter, the present invention will be described in more detail based on Examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not construed as limiting by the examples shown below.

[Colorant]
Each colorant was prepared by the following method.

<Titanium Nitride-Containing Particles (TiN-1)>
First, Ti particles (TC-200, manufactured by Toho Tech Co., Ltd.) were plasma-treated in Ar gas to form Ti nanoparticles. The Ti nanoparticles after plasma treatment, _{O 2} concentration 50ppm or less under an Ar gas atmosphere, and allowed to stand for 24 hours under conditions of 30 ° C.. Then, it was allowed to stand at 30 ° C. for 24 hours in a state _{where O 2} gas was introduced into an Ar atmosphere so that the O ₂ concentration became 100 ppm (pretreatment of Ti particles).
Then, the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition that the yield was 10% to obtain a powder of Ti particles. The primary particle size of the obtained powder was 120 nm when the average particle size of 100 particles was determined by arithmetic mean by TEM observation.
The titanium nitride-containing particles TiN-1 were produced using an apparatus similar to the black composite fine particle producing apparatus described in FIG. 1 of International Publication No. 2010/147098.
Specifically, in the black composite fine particle manufacturing apparatus, high-frequency voltages of about 4 MHz and about 80 kVA are applied to the high-frequency oscillation coil of the plasma torch, and argon gas 50 L / min and nitrogen 50 L / min are applied as plasma gas from the plasma gas supply source. The mixed gas of Argon-nitrogen was generated in the plasma torch. 10 L / min of carrier gas was supplied from the spray gas supply source of the material supply device.
Fe powder (JIP270M, manufactured by JFE Steel) and Si powder (Silicon powerer SI006031) have a mass ratio of Ti / Fe / Si = residue / 0 with respect to the Ti particles obtained as described above. The mixture was mixed so as to be 0.05 / 0.05. This mixture was supplied into a thermal plasma flame in a plasma torch together with argon gas as a carrier gas, evaporated in the thermal plasma flame, and highly dispersed in a vapor phase state.
Further, nitrogen was used as the gas supplied into the chamber by the gas supply device. At this time, the flow velocity in the chamber was 5 m / sec, and the supply amount was 1,000 L / min. The pressure inside the cyclone was set to 50 kPa, and the supply speed of each raw material from the chamber to the cyclone was set to 10 m / s (average value).
In this way, titanium nitride-containing particles TiN-1 were obtained.

The contents of titanium (Ti) atom, iron (Fe) atom and silicon (Si) atom of the obtained titanium nitride-containing particles TiN-1 were measured by ICP emission spectroscopic analysis. For the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analyzer "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used.
The nitrogen atom content was measured using an oxygen / nitrogen analyzer "EMGA-620W / C" (trade name) manufactured by Horiba Seisakusho, and calculated by the inert gas melting-thermal conductivity method. As a result of the above, the mass ratio of each atom contained in the titanium nitride-containing particles TiN was Ti / N / Fe / Si = 57/34 / 0.0030 / 0.0020.

The X-ray diffraction of the titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (manufactured by Rigaku Denki Co., Ltd., trade name "RU-200R") in which a powder sample was packed in an aluminum standard sample holder. As the measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was set to 2 ° / min.
Then, the diffraction angle of the peak derived from the TiN (200) plane observed near the diffraction angle 2θ (42.6 °) was measured. Furthermore, from the half width of the peak derived from the (200) plane, the crystallite size constituting the particles was determined using Scheller's equation. As a result, the peak diffraction angle was 42.62 ° and the crystallite size was 10 nm. No X-ray diffraction peak due to _{TiO 2 was observed.}

<Titanium Nitride-Containing Particles TiN-2>
As Ti particles, instead of "TC-200" manufactured by Toho Tech Co., Ltd., "578347" manufactured by Sigma Aldrich Co., Ltd. is used, and the mass ratios of Fe powder and Si powder are Ti / Fe / Si = residue /. Titanium nitride-containing particles TiN-2 were obtained in the same manner as TiN-1 except that they were mixed so as to be 0.5 / 1.
The peak diffraction angle measured by X-ray diffraction was 42.81 °, and the crystallite size was 12 nm.

<Titanium Nitride-Containing Particles TiN-3>
Titanium nitride-containing particles TiN-3 were obtained in the same manner as TiN-1 except that Fe powder and Si powder were mixed so that their mass ratios were Ti / Fe / Si = residue / 1/2. It was.
The peak diffraction angle measured by X-ray diffraction was 43.1 °, and the crystallite size was 12 nm.

<Making Titanium Black A-1>
100 g of titanium oxide MT-150A (trade name, manufactured by TAYCA CORPORATION) with an average particle size of 15 nm, ^{and silica particles with a BET (Brunauer, Emmett, Teller) specific surface area of 300 m 2} / g AEROSIL300 (registered trademark) 300/30 (Ebonic Weighed 25 g of (manufactured by BIC) and 100 g of Disperbyk190 (trade name, manufactured by Big Chemie), and added these to 71 g of ion-electrically exchanged water to obtain a mixture. Then, using MAZERSTAR KK-400W manufactured by KURABO, the mixture was treated at a revolution speed of 1,360 rpm and a rotation speed of 1,047 rpm for 30 minutes to obtain a uniform aqueous mixture solution. The aqueous mixture solution was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Then, the inside of the small rotary kiln was replaced with nitrogen, and the nitriding reduction treatment was carried out by flowing ammonia gas at 100 mL / min at the same temperature for 5 hours. After completion, the recovered powder was pulverized in a mortar to obtain a powdery titanium black [titanium black particles and a dispersion containing Si atoms] having ^{a specific surface area of 73 m 2 / g containing Si atoms (hereinafter, "titanium").} Black A-1 ").

<Preparation of Niobium Nitride-Containing Particles (NbN) Containing Fe Atoms>
Niobium nitride-containing particles containing Fe atoms were prepared by the following method.
First, niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemical Co., Ltd. was prepared as a raw material (hereinafter, also referred to as "metal raw material powder").
Next, the metal raw material powder was plasma-treated in Ar gas to form Nb nanoparticles. The conditions of the plasma treatment were in accordance with the following plasma treatment (1).

(Plasma processing (1))
Plasma treatment (1) was carried out by the following method. Plasma treatment (1) was carried out under the following conditions using an apparatus similar to the above-mentioned black composite fine particle production apparatus.
-High frequency voltage applied to the high frequency oscillation coil: frequency approx. 4 MHz, voltage approx. 80 kVA
-Plasma gas: Argon gas (supply amount 100 L / min)
-Carrier gas: Argon gas (supply amount 10 L / min)
-Chamber atmosphere: Argon gas (supply amount 1,000 L / min, chamber flow velocity 5 m / sec)
・ Atmosphere inside the cyclone: Argon gas, internal pressure 50 kPa
-Material supply speed from the chamber to the cyclone: 10 m / s (average value)

Next, Fe powder (JIP270M, manufactured by JFE Steel) was prepared and subjected to plasma treatment under the conditions of plasma treatment (1) to form Fe nanoparticles.

Next, the Nb nanoparticles and Fe nanoparticles obtained above were mixed to obtain a raw metal powder. Niobium nitride-containing particles were obtained by plasma-treating this raw metal powder in nitrogen gas. The conditions for the plasma treatment were in accordance with the following plasma treatment (2).

(Plasma processing (2))
Plasma treatment (2) was carried out by the following method. The apparatus used was the same as that of the plasma treatment (1).
-High frequency voltage applied to the high frequency oscillation coil: frequency approx. 4 MHz, voltage approx. 80 kVA
-Plasma gas: Argon gas and nitrogen gas (supply amount 50 L / min each)
-Carrier gas: Nitrogen gas (supply amount 10 L / min)
-Chamber atmosphere: Nitrogen gas (supply amount 1,000 L / min, chamber flow velocity 5 m / sec)
・ Atmosphere inside the cyclone: Nitrogen gas, internal pressure 50 kPa
-Material supply speed from the chamber to the cyclone: 10 m / s (average value)

After the plasma treatment (2) is completed, Nitrogen gas at 20 ° C. is introduced into the particles using Ar gas using Ar gas using a split flow type humidity supply device SRH manufactured by Nippon Shintec Co., Ltd. under the condition that the relative humidity is 95% in the atmosphere. I left it for a while. Then, the obtained particles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition that the yield was 10% to obtain niobium nitride-containing particles (NbN). Nitrogen gas was supplied to the separator.
The content of iron (Fe) atoms of the obtained niobium nitride-containing particles was measured by ICP emission spectroscopic analysis and found to be 50 mass ppm.

<Preparation of vanadium nitride-containing particles (VN) containing Fe atoms>
In the production of niobium nitride-containing particles containing Fe atoms, the Fe atoms were similarly prepared except that the metal vanadium powder VHO manufactured by Taiyo Mining Co., Ltd. was used instead of the niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemicals. Vanadium nitride-containing particles (VN) containing the above were prepared. The content of iron (Fe) atoms of the obtained vanadium nitride-containing particles was measured by ICP emission spectroscopic analysis and found to be 50 mass ppm.

[Polyfunctional thiol compound]
The following SH-4, SH-3, and SH-2 were used as the polyfunctional thiol compound.

SH-4 (corresponds to pentaerythritol tetra (3-mercaptopropionate), a tetrafunctional thiol compound)

SH-3 (corresponds to trimethylolpropane tris (3-mercaptopropionate), a trifunctional thiol compound)

SH-2 (corresponds to 1,4-butanediol bis (thioglycolate), a bifunctional thiol compound)

[Dispersant]
As the dispersant, dispersant A having the following structure was used. The numerical value described in each structural unit is intended to be the mass% of each structural unit with respect to all the structural units.

・ Dispersant A

[Binder resin]
The following resin A was used as the binder resin. The numbers given for each structural unit are intended to be mol% of each structural unit relative to all structural units. In the formula of resin A, each abbreviation represents the following.
BzMA: Benzyl methacrylate MMA: Methyl methacrylate

・ Resin A

[Polymerizable compound]
-Polymerizable compound M1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD", refer to the following formula)

[Photopolymerization initiator]
・ OXE-01: Irgacare OXE01 (trade name, manufactured by BASF Japan Ltd.)

-OXE-02: Irgacare OXE02 (trade name, manufactured by BASF Japan Ltd.)

PI-3: Photopolymerization initiator having the following structure

・ NCI-831 (trade name, manufactured by ADEKA Corporation)

-IRG-379: IRGACURE 379 (trade name, manufactured by BASF Japan Ltd.)

[Polymerization inhibitor]
Ih-1: 4-methoxyphenol Ih-2: 2,6-di-tert-butyl-4-methylphenol Ih-3: 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical

[Surfactant]
F-1: Compound represented by the following formula (weight average molecular weight (Mw) = 15,311)
However, in the following formula, the structural units represented by the formulas (A) and (B) are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a, b, and c satisfy the relations of a + c = 14 and b = 17, respectively.

〔Organic solvent〕
・ PGMEA: Propylene glycol monomethyl ether acetate ・ Cyclopentanone ・ Butyl acetate

[Preparation of colorant dispersion]
First, the colorant, the dispersant and the organic solvent were mixed with a stirrer (Eurostar manufactured by IKA) for 15 minutes to obtain a mixed solution of the above components. Next, the obtained mixed solution was subjected to a dispersion treatment using NPM-Pilot manufactured by Simul Enterprises under the following conditions to obtain a colorant dispersion.

<Dispersion condition>
-Bead diameter: φ0.05 mm, (Nikkato zirconia beads, YTZ)
-Bead filling rate: 65% by volume
・ Mill peripheral speed: 10 m / sec
・ Separator peripheral speed: 13 m / s
-Amount of mixed liquid to be dispersed: 15 kg
・ Circulation flow rate (pump supply amount): 90 kg / hour
-Treatment liquid temperature: 19 to 21 ° C
・ Cooling water: Water ・ Treatment time: About 22 hours

[Preparation of curable composition]
Next, the colorant dispersion, the polyfunctional thiol compound, the binder resin, the polymerizable compound, the polymerization initiator, the polymerization inhibitor, and the surfactant are mixed and stirred, and the following Tables 1-1 and 1-2 are mixed and stirred. And each curable composition of Examples and Comparative Examples shown in Table 2 was obtained. The content of each component in Table 1-1, Table 1-2, and Table 2 is mass%.
The final solid content of each curable composition was adjusted with an organic solvent so as to have the solid content concentration shown in Table 1-1, Table 1-2 and Table 2. Further, the organic solvent was used in combination so that the mass ratio of each curable composition was PGMEA / butyl acetate / cyclohexanone = 27/18/27.

[Evaluation]
The following evaluation tests were carried out for each of the curable compositions of Examples and Comparative Examples. The results are summarized in Table 1-1 and Table 1-2.

[OD value]
A coating film was formed by spin coating on a glass plate (EagleXG, manufactured by Corning Inc.) having a thickness of 0.7 mm and a square of 10 cm using each curable composition. At this time, the rotation speed was adjusted so that a cured film having a film thickness of 1.5 μm could be obtained. The formed coating film was dried on a hot plate by heat treatment at 100 ° C. for 2 minutes and exposed at an exposure amount of ^{500 mJ / cm 2 to obtain a cured film.} The OD value of the obtained glass substrate containing the cured film was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The larger the OD value, the better the light-shielding property of the cured film. The results are summarized in Table 1-1, Table 1-2 and Table 2.
The OD values shown in Table 1-1, Table 1-2, and Table 2 are the minimum values at wavelengths of 400 to 800 nm. That is, the cured film (thickness 1.5 μm) of each example has an OD value equal to or higher than the OD values shown in Table 1-1, Table 1-2, and Table 2 over the entire wavelength range of 400 to 800 nm.

[Pattern shape]
Each curable composition was used on a Si substrate, the rotation speed was adjusted so that a cured film having a film thickness of 1.5 μm could be obtained, and a coating film was formed by spin coating. The formed coating film was dried on a hot plate by heat treatment at 100 ° C. for 2 minutes to obtain a cured film. With respect to the obtained Si substrate containing the cured film, an i-line stepper (FPA3000i5 + manufactured by Canon) was used on the prebaked substrate with a coating film, and a photomask having a length of 200 μm × width of 20 μm was formed through a photomask. The coating film was exposed at the exposure amounts shown in the table. The coating film after exposure was paddle-developed with a coater developer ACT8 manufactured by Tokyo Electron for 30 seconds using tetramethylammonium hydroxide as a developing solution. After the development, a shower rinse treatment was carried out with pure water for 20 seconds. The developed coating film was post-baked (temperature: 220 ° C., time: 300 seconds). The pattern shape of the coating film after post-baking was measured by a length measuring SEM (Scanning Electron Microscope). Specifically, the film thickness at the edge of the line pattern and the film thickness at the center were measured, the ratio (film thickness at the edge of the pattern / film thickness at the center) was calculated, and the evaluation was made according to the following criteria. The results are summarized in Table 1-1, Table 1-2 and Table 2. A practical range of evaluation "2" or higher is.
7: The ratio is more than 0.98 and 1.00 or less, and there is no difference in the film thickness between the central portion and the edge portion of the pattern when observed by SEM.
-6: The ratio is more than 0.96 and 0.98 or less, and there is a slight difference in the film thickness between the central portion and the edge portion of the pattern.
5: The ratio is more than 0.94 and 0.96 or less, and there is a difference in the film thickness between the central portion and the end portion of the pattern.
-4: The ratio is more than 0.92 and 0.94 or less, the film thickness at the end is thin, and it is slightly distorted, but there is no problem in practical use.
-3: The ratio is more than 0.90 and 0.92 or less, and the film thickness at the end is thin and distorted, but there is no problem in practical use.
-2: The ratio is more than 0.80 and 0.90 or less, and the film thickness at the end is thin, but it is a practical level.
-1: The ratio is 0.80 or less, the film thickness at the end is thin, and it is unacceptable.

[Stability over time]
Each curable composition after preparation was sealed in a 100 cc bloom bottle and stored in a constant temperature bath at 45 ° C. for 7 days. Then, the pattern shape was evaluated by the same method as described above. The results are shown in Table 2.

From the results shown in Table 1-1 and Table 1-2, it is a curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound. A cured film obtained by curing the curable composition of each example having an optical density of 4.0 or more per 1.5 μm film thickness in the visible light region of the cured film obtained by curing an object. Had an excellent pattern shape. On the other hand, the curable composition of Comparative Example did not have a desired effect.
The curable composition of Example 48, wherein the content of the colorant is 55% by mass or more with respect to the total solid content of the curable composition, has the same content of the dispersant and contains the colorant. The pattern shape of the obtained cured product was more excellent than that of the curable composition of Example 49 in which the amount was 53%.
The curable compositions of Examples 1, 2 and 3 in which the content of the polyfunctional thiol compound is 1 to 5.5% by mass with respect to the content of the colorant are the curable compositions of Example 4. The pattern shape of the obtained cured product was superior to that of the curable composition.
The curable composition of Example 45, which contains two or more phenolic compounds as a polymerization inhibitor, is cured at a lower exposure amount than the curable composition of Example 36, and has a pattern of the cured product. The shape was excellent.
The curable composition of Example 46 containing a phenolic compound and a hindered amine compound as a polymerization inhibitor was cured at a lower exposure amount as compared with the curable composition of Example 36, and the pattern shape of the cured product was obtained. Was excellent.
The curable composition of Example 5 in which the polyfunctional thiol compound was trifunctional had a more excellent pattern shape of the cured product as compared with the curable composition of Example 9.
The curable composition of Example 1 in which the polyfunctional thiol compound was tetrafunctional had a more excellent pattern shape of the cured product as compared with the curable compositions of Examples 9 and 5.
The curable composition of Example 34 in which the photopolymerization initiator was an oxime compound had a more excellent pattern shape of the cured product as compared with the curable composition of Example 25.
The curable compositions of Examples 13 and 48, wherein the content of the photopolymerization initiator is more than 1% by mass and less than 10% by mass with respect to the total solid content of the curable composition, are described in Examples 50 and Example. The pattern shape of the cured product was more excellent than that of the curable composition of 51.
The curable compositions of Examples 13 and 48, wherein the content of the polymerizable compound is more than 3.5% by mass and less than 20% by mass with respect to the total solid content of the curable composition, are described in Examples 50 and Example. The pattern shape of the cured product was more excellent than that of the curable composition of Example 51.
The curable compositions of Examples 2 and 48 having a dispersant content of 17% by mass or more have a pattern shape of the cured product as compared with the curable compositions of Examples 13 and 54. It was better.

In Example 1, a curable composition was prepared in the same manner except that the surfactant F-1 was not used, and evaluation was carried out using this. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

[Preparation of carbon black dispersion (CB dispersion) and evaluation of curable composition]
In the preparation of the above colorant dispersion, the colorant was carbon black (trade name "Color Black S170", manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m ² / g, carbon produced by the gas black method. A carbon black dispersion (CB dispersion) was obtained by the same method except that it was black).

In the preparation of the curable composition of Example 1, the titanium nitride-containing particles TiN were replaced with the colorant dispersion liquid to which the titanium nitride-containing particles TiN-1 were added so as to contain 58% by mass in the curable composition. A mixture of the colorant dispersion liquid containing -1 and the above-mentioned CB dispersion liquid (titanium nitride-containing particles TiN-1 in the curable composition: carbon black in the curable composition = 45: 13 (mass ratio). ), The total content of the titanium nitride-containing particles TiN-1 and carbon black in the curable composition is 58% by mass), and a curable composition is prepared in the same manner. Was evaluated using. As a result of the evaluation, it was found that the same light-shielding property and pattern shape as in Example 1 could be obtained.

[Preparation of chromatic pigment dispersion (PY dispersion) and evaluation of curable composition]
In the preparation of the above colorant dispersion liquid, the chromatic pigment dispersion was prepared by the same method except that the colorant was Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 pigment yellow 5GN). (PY dispersion liquid) was obtained.

In the preparation of the curable composition of Example 1, the titanium nitride-containing particles TiN were replaced with the colorant dispersion liquid to which the titanium nitride-containing particles TiN-1 were added so as to contain 58% by mass in the curable composition. A mixture of the colorant dispersion liquid containing -1 and the above PY dispersion liquid (titanium nitride-containing particles TiN-1 in the curable composition: pigment yellow 150 = 45: 13 in the curable composition (mass ratio). ), The total content of the titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the curable composition is 58% by mass.) Was evaluated using. As a result of the evaluation, it was found that the same light-shielding property and pattern shape as in Example 1 were obtained, and a darker blackish film was obtained.

[Preparation of chromatic pigment dispersion (PR dispersion)]
In the preparation of the above colorant dispersion, the colorant was used as C.I. I. A chromatic pigment dispersion (PR dispersion liquid) was obtained by the same method except that Pigment Red 254 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was used.

[Preparation of chromatic pigment dispersion (PB dispersion)]
In the preparation of the above colorant dispersion, the colorant was used as C.I. I. A chromatic pigment dispersion (PB dispersion liquid) was obtained by the same method except that Pigment Blue 15: 6 (manufactured by DIC Corporation) was used.

[Preparation of chromatic pigment dispersion (PV dispersion)]
In the preparation of the above colorant dispersion, the colorant was used as C.I. I. A chromatic pigment dispersion (PV dispersion liquid) was obtained by the same method except that Pigment Violet 23 (manufactured by Clariant AG) was used.

In the preparation of the curable composition of Example 1, the above-mentioned titanium nitride-containing particles were contained in place of the colorant dispersion liquid to which the titanium nitride-containing particles TiN-1 were added so as to contain 58% by mass in the curable composition. Mixture with particles TiN-1, PY, PR, PB, and PV dispersion (ratio of titanium nitride-containing particles TiN-1, PY, PR, PB, and PV in the curable composition; titanium nitride-containing particles TiN-1: PY: PR: PB: PV = 70: 17: 37: 36: 10 (mass ratio) of titanium nitride-containing particles TiN-1, PY, PR, PB, and PV in the curable composition. A curable composition was prepared in the same manner except that the total content was 58% by mass.), And the evaluation was carried out using this. As a result of the evaluation, it was found that a film having the same light-shielding property as in Example 1 and a pattern shape similar to that of Example 1 was obtained, and further, a film having excellent light-shielding property in the infrared region could be obtained.

In the preparation of the curable composition of Example 1, the above-mentioned titanium nitride-containing particles were contained in place of the colorant dispersion liquid to which the titanium nitride-containing particles TiN-1 were added so as to contain 58% by mass in the curable composition. Mixture of particles TiN-1 and compound SQ-23 shown below (ratio of titanium nitride-containing particles TiN-1 and compound SQ-23 in the curable composition; titanium nitride-containing particles TiN-1: compound SQ The same applies except that -23 = 50: 8 (mass ratio), the total content of the titanium nitride-containing particles TiN-1 in the curable composition, and the compound SQ-23 is 58% by mass). A curable composition was prepared and evaluated using it. As a result of the evaluation, it was found that a film having the same light-shielding property as in Example 1 and a pattern shape similar to that of Example 1 was obtained, and further, a film having excellent light-shielding property in the infrared region could be obtained.

In the preparation of the curable composition of Example 1, the above-mentioned titanium nitride-containing particles were contained in place of the colorant dispersion liquid to which the titanium nitride-containing particles TiN-1 were added so as to contain 58% by mass in the curable composition. Mixture of particles TiN-1 and the following compound A-52 (ratio of titanium nitride-containing particles TiN-1 and compound A-52 in the curable composition; titanium nitride-containing particles TiN-1: compound A-52) = 50: 8 (mass ratio), the total content of the titanium nitride-containing particles TiN-1 in the curable composition and compound A-52 is 58% by mass), and the like is cured in the same manner. A sex composition was prepared and evaluated using it. As a result of the evaluation, it was found that a film having the same light-shielding property as in Example 1 and a pattern shape similar to that of Example 1 was obtained, and further, a film having excellent light-shielding property in the infrared region could be obtained.

Compound SQ-23

Compound A-52

101 Support 102 Curable composition layer 103 Photomask 201 Hardened film 301 Hardened film after post-baking 401 Curable composition layer 402 Mask light-shielding part 501 Hardened film 601 Hardened film after post-baking

Claims (34)

A curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, and a polyfunctional thiol compound.
The optical density of the cured film obtained by curing the curable composition per 1.5 μm film thickness in the visible light region is 4.0 or more.
The colorant contains titanium nitride-containing particles and
The titanium nitride-containing particles contain at least one atom selected from the group consisting of Fe atoms and Si atoms.
When the titanium nitride-containing particles contain Fe atoms, the content of the Fe atoms in the titanium nitride-containing particles is more than 0.001% by mass with respect to the total mass of the titanium nitride-containing particles. Less than 4% by mass,
When the titanium nitride-containing particles contain Si atoms, the content of the Si atoms in the titanium nitride-containing particles is more than 0.002% by mass with respect to the total mass of the titanium nitride-containing particles. A curable composition that is less than 3% by weight. A curable composition containing a colorant, a photopolymerization initiator, a polymerizable compound, a polyfunctional thiol compound, and a polymerization inhibitor.
The optical density of the cured film obtained by curing the curable composition per 1.5 μm film thickness in the visible light region is 4.0 or more.
The polymerization inhibitor contains two or more kinds of phenolic compounds, or contains a phenolic compound and a hindered amine compound .
When the polymerization inhibitor contains two or more kinds of phenolic compounds, the polymerization inhibitor is a compound represented by the following formula (IH-1), and R ₁ and R ₅ are each independently hydrogen. The first phenolic compound representing an atom or a tert-butyl group, R ₂ and R ₄ representing a hydrogen atom, and R ₃ representing a methoxy group or an ethoxy group, and the following formula (IH-1). A second compound in which R ₁ and R ₅ independently represent a hydrogen atom or a tert-butyl group, R ₂ and R ₄ represent a hydrogen atom, and R ₃ represents a methyl or ethyl group. Containing at least a phenolic compound,

When said polymerization inhibitor contains phenolic compounds and hindered amine compounds, the polymerization inhibitor, with the first phenol compound is a compound represented by the following formula (IH-2), R ₆ Is a curable composition containing at least a hindered amine compound, which represents a hydrogen atom or a hydroxy group, and R _{7 to} R _{10 each independently represent a methyl group or an ethyl group.}

The curable composition according to claim 2, wherein the polymerization inhibitor contains 4-methoxyphenol and 2,6-di-tert-butyl-4-methylphenol. The curable composition according to claim 2 or 3, wherein the polymerization inhibitor contains 4-methoxyphenol and 4-hydroxy-2,2,6,6-tetramethylpiperidin1-oxylfree radical. A colorant, a photopolymerization initiator, a polymerizable compound, a curable composition comprising a multifunctional thiol compound,
The optical density of the cured film obtained by curing the curable composition per 1.5 μm film thickness in the visible light region is 4.0 or more.
The polyfunctional thiol compound is pentaerythritol tetra (3-mercaptopropionate).
The colorant is at least one selected from the group consisting of metal pigments containing titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin, and metal pigments containing silver and tin. Ri,
The pentagonal content of pentaerythritol tetra (3-mercaptopropionate), Ru 1-10% by mass relative to the content of the coloring agent, the curable composition. The curable composition according to any one of claims 2 to 4, wherein the colorant is an inorganic pigment. The inorganic pigment contains at least one selected from the group consisting of a metal pigment containing titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin, and a metal pigment containing silver and tin. The curable composition according to claim 6. The curable composition according to claim 1 or 5, further comprising a polymerization inhibitor. The curable composition according to claim 8 , wherein the polymerization inhibitor contains a phenolic compound. The curable composition according to claim 8 or 9 , wherein the polymerization inhibitor contains two or more kinds of phenolic compounds. The curable composition according to any one of claims 8 to 10 , wherein the polymerization inhibitor contains a hindered amine compound. The curing according to any one of claims 2 to 4 and 8 to 10, wherein the content of the polymerization inhibitor is 0.1 to 1.5% by mass with respect to the content of the polyfunctional thiol compound. Sex composition. The curable composition according to any one of claims 1, 2 to 4 , 6 and 7 , wherein the polyfunctional thiol compound is a compound having two or more groups represented by the formula (1).

In formula (1), L ¹ represents a single bond or −CO−, and L ² represents a single bond or a divalent linking group. The curable composition according to any one of claims 1, 2 to 4, 6, 7 and 13 , wherein the polyfunctional thiol compound is trifunctional or higher. The polyfunctional thiol compound is at least one selected from the group consisting of pentaerythritol tetra (3-mercaptopropionate) and trimethylolpropanetris (3-mercaptopropionate), claim 1. 2. The curable composition according to any one of 4, 6, 7, 13 and 14. The curable composition according to any one of claims 1 to 15 , wherein the photopolymerization initiator is an oxime compound. The curable composition according to claim 16 , wherein the oxime compound is an oxime compound containing a fluorine atom. The curable composition according to claim 17 , wherein the oxime compound containing a fluorine atom is a compound having the following structure.

The curable composition according to any one of claims 1 to 18 , wherein the colorant further contains an infrared absorber. The curable composition according to claim 19 , wherein the infrared absorber contains at least one selected from the group consisting of a pyrrolopyrrole compound and a squarylium compound. The curable composition according to any one of claims 1 to 20 , wherein the content of the colorant is 55% by mass or more with respect to the total solid content of the curable composition. The curable composition according to any one of claims 1 to 21 , wherein the content of the polyfunctional thiol compound is 1 to 5.5% by mass with respect to the content of the colorant. The curable composition according to any one of claims 1 to 22 , wherein the content of the photopolymerization initiator is more than 1% by mass and less than 10% by mass with respect to the total solid content of the curable composition. Stuff. The curability according to any one of claims 1 to 23 , wherein the content of the polymerizable compound is more than 3.5% by mass and less than 20% by mass with respect to the total solid content of the curable composition. Composition. The curability according to any one of claims 1 to 24 , further containing a dispersant, wherein the content of the dispersant is 17% by mass or more with respect to the total solid content of the curable composition. Composition. A cured film obtained by curing the curable composition according to any one of claims 1 to 25. A color filter containing the cured film according to claim 26. A light-shielding film containing the cured film according to claim 26. A solid-state imaging device containing the cured film according to claim 26. An image display device containing the cured film according to claim 26. A curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of claims 1 to 25.
A method for producing a cured film containing an exposure step of exposing the curable composition layer. The method for producing a cured film according to claim 31 , wherein the exposure amount of the curable composition layer in the exposure step is 200 mJ / cm ² or more. 31 or 32 , wherein the curable composition layer forming step includes a coating step of directly coating the curable composition on the support to form the curable composition layer on the support. The method for producing a cured film according to. Further, a developing step of developing the exposed curable composition layer, and
The method for producing a cured film according to any one of claims 31 to 33 , which comprises a washing step of washing the developed curable composition layer.

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